Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

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

Jiang, Tingshun, E-mail: tshjiang@mail.ujs.edu.cn; Cheng, Jinlian; Liu, Wangping

2014-10-15

Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH{sub 3}-TPD and N{sub 2} physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 still have good mesoporous structure and long rangemore » ordering. Compared with the Zr (or Al)–MCM-48 samples, SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO{sub 4}{sup 2−}/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h{sup −1} and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO{sub 4}{sup 2−}/Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO{sub 4}{sup 2−}/Zr-MCM-48-25.« less

Synthesis and evaluation of new antimalarial analogues of quinoline alkaloids derived from Cinchona ledgeriana Moens ex Trimen.

PubMed

Park, Byeoung-Soo; Kim, Dae-Young; Rosenthal, Philip J; Huh, Sun-Chul; Lee, Belinda J; Park, Eun -u; Kim, Sung-Min; Kim, Jang-Eok; Kim, Mi-Hee; Huh, Tae-Lin; Choi, Young-Jae; Suh, Ki-Hyung; Choi, Won-Sik; Lee, Sung-Eun

2002-05-20

In the course of attempts to develop antimalarial drugs, we have designed and synthesized a series of quinoline alkaloide derivatives. Three of them, N-(4-methoxy-3,5-di-tert-butylbenzyl)cinchonidinium bromide (OSL-5), O-benzyl-N-(3,5-di-tert-butyl-4-methoxybenzyl)cinchonidinium bromide (OSL-7), and N-(3,5-di-tert-butyl-4-methoxybenzyl)quininium bromide (OSL-14) show potent activity against Plasmodium falciparum.

40 CFR 464.41 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (dichloromethane) 65. phenol 66. bis(2-ethylhexyl) phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 85.... naphthalene 65. phenol 66. bis (2-ethylhexyl) phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 85...) 55. naphthalene 65. phenol 66. bis(2-ethylhexyl) phthalate 68. di-n-butyl phthalate 85...

40 CFR 464.41 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... (dichloromethane) 65. phenol 66. bis(2-ethylhexyl) phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 85.... naphthalene 65. phenol 66. bis (2-ethylhexyl) phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 85...) 55. naphthalene 65. phenol 66. bis(2-ethylhexyl) phthalate 68. di-n-butyl phthalate 85...

Probing the electronic structure of platinum(II) chromophores: crystal structures, NMR structures, and photophysical properties of six new bis- and di- phenolate/thiolate Pt(II)diimine chromophores.

PubMed

Weinstein, Julia A; Tierney, Mark T; Davies, E Stephen; Base, Karel; Robeiro, Anthony A; Grinstaff, Mark W

2006-05-29

A general route for synthesis of six structurally similar Pt(II) diimine thiolate/phenolates chromophores possessing bulky phenolate or thiolate ligands is reported. The Pt chromophores were characterized using an array of techniques including 1H, 13C, and 195Pt NMR, absorption, emission, (spectro)electrochemistry, and EPR spectroscopy. Systematic variation of the electronic structure of the Pt(II) chromophores studied was achieved by (i) changing solvent polarity; (ii) substituting oxygen for sulfur in the donor ligand; (iii) alternating donor ligands from bis- to di-coordination; and (iv) changing the electron donating/withdrawing properties of the ligand(s). The lowest excited state in these new chromophores was assigned to a [charge-transfer-to-diimine] transition from the HOMO of mixed Pt/S (or Pt/O) character on the basis of absorption and emission spectroscopy, UV/vis (spectro)electrochemistry, and EPR spectroscopy. One of the chromophores, Pt(dpphen)(3,5-di-tert-butyl-catecholate) represents an example of a Pt(II) diimine phenolate chromophore that possesses a reversible oxidation centered predominantly on the donor ligand. Results from EPR spectroscopy indicate participation of the Pt(II) orbitals in the HOMO. There is a dramatic difference in the photophysical properties of carborane complexes compared to other mixed-ligand Pt(II) compounds, which includes room-temperature emission and photostability. The charge-transfer character of the lowest excited state in this series of chromophores is maintained throughout. Moreover, the absorption and emission energies and the redox properties of the excited state can be significantly tuned.

40 CFR 464.11 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (dichloromethane) 65. phenol 66. bis(2-ethylhexyl) phthalate 67. butyl benzyl phthalate 84. pyrene 85... 65. phenol 66. bis(2-ethylhexyl) phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70...) 65. phenol 66. bis (2-ethylhexyl) phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 73. benzo...

Effects of the GABAB Receptor-Positive Modulators CGP7930 and rac-BHFF in Baclofen- and γ-Hydroxybutyrate-Discriminating Pigeons

PubMed Central

France, Charles P.; Cheng, Kejun; Rice, Kenner C.

2012-01-01

In vivo effects of GABAB receptor-positive modulators suggest them to have therapeutic potential to treat central nervous system disorders such as anxiety and drug abuse. Although these effects are thought to be mediated by positive modulation of GABAB receptors, such modulation has been examined primarily in vitro. This study further examined the in vivo properties of the GABAB receptor-positive modulators 2,6-di-tert-butyl-4-(3-hydroxy-2,2-dimethylpropyl) phenol (CGP7930) and (R,S)-5,7-di-tert-butyl-3-hydroxy-3-trifluoromethyl-3H-benzofuran-2-one (rac-BHFF). In pigeons discriminating baclofen from saline, γ-hydroxybutyrate (GHB) produced 100% baclofen-appropriate responding, and the GABAB antagonist 3-aminopropyl(dimethoxymethyl) phosphinic acid (CGP35348) blocked the effects of both drugs. CGP7930 and rac-BHFF produced at most 41 and 74% baclofen-appropriate responding, respectively, and enhanced the discriminative stimulus effects of baclofen, but not of GHB. In pigeons discriminating GHB from saline, CGP7930 and rac-BHFF produced at most 1 and 49% GHB-appropriate responding, respectively, and enhanced the effects of baclofen, but not of GHB. Enhancement of the discriminative stimulus effects of baclofen by rac-BHFF and CGP7930 is further evidence of their effectiveness as GABAB receptor-positive modulators in vivo. Furthermore, lack of complete substitution of the positive modulators rac-BHFF and CGP7930 for baclofen and GHB suggests that their discriminative stimulus effects differ from those of GABAB receptor agonists. Finally, together with converging evidence that the GABAB receptor populations mediating the effects of baclofen and GHB are not identical, the present findings suggest that these populations differ in their susceptibility to positive modulatory effects. Such differences could allow for more selective therapeutic targeting of the GABAB system. PMID:22319197

Composition and method for encapsulating photovoltaic devices

DOEpatents

Pern, Fu-Jann

2000-01-01

A composition and method for encapsulating a photovoltaic device which minimizes discoloration of the encapsulant. The composition includes an ethylene-vinyl acetate encapsulant, a curing agent, an optional ultraviolet light stabilizer, and/or an optional antioxidant. The curing agent is preferably 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane; the ultraviolet light stabilizer is bis-(N-octyloxy-tetramethyl) piperidinyl sebacate and the antioxidant is selected from the group consisting of tris (2,4-di-tert-butylphenyl) phosphite, tetrakis methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, and 2,2'-ethylidene bis(4,6-di-t-butylphenyl) fluorophosponite. The composition is applied to a solar cell then cured. The cured product contains a minimal concentration of curing-generated chromophores and resists UV-induced degradation.

Congested ferrocenyl polyphosphanes bearing electron-donating or electron-withdrawing phosphanyl groups: assessment of metallocene conformation from NMR spin couplings and use in palladium-catalyzed chloroarenes activation.

PubMed

Mom, Sophal; Beaupérin, Matthieu; Roy, David; Royer, Sylviane; Amardeil, Régine; Cattey, Hélène; Doucet, Henri; Hierso, J-C

2011-11-21

The synthesis of novel substituted cyclopentadienyl salts that incorporate both a congested branched alkyl group (tert-butyl, (triphenyl)methyl, or tri(4-tert-butyl)phenylmethyl) and a phosphanyl group is reported. The introduction of either electron-withdrawing or electron-donating substituents (furyl, i-propyl, cyclohexyl, tert-butyl) on P atoms was generally achieved in high yield. The modular synthesis of ferrocenyl polyphosphanes from an assembly of these cyclopentadienyl salts was investigated, leading to the formation of new triphosphanes (denoted as 9-12) and diphosphanes (denoted as 14-16). The resulting phosphanes are not sensitive to air or moisture, even when electron-rich substituents are present. This set of polyphosphanes displays varied conformational features, which are discussed in the light of their multinuclear NMR characterization in solution and of the X-ray solid state structure of the representative triphosphane 1,2-bis(diphenylphosphanyl)-1'-(diisopropylphosphanyl)-3'-(triphenyl)methyl-4-tert-butyl ferrocene, 11. In particular, the existence of a range of significantly different nonbonded ("through-space", TS) spin-spin coupling constants between heteroannular P atoms, for the triphosphanes of this class, allowed their preferred conformation in solution to be appraised. The study evidences an unanticipated flexibility of the ferrocene platform, despite the presence of very congested tert-butyl and trityl groups. Herein, we show that, contrary to our first belief, the preferred conformation for the backbone of ferrocenyl polyphosphanes can not only depend on the hindrance of the groups decorating the cyclopentadienyl rings but is also a function of the substituents of the phosphanyl groups. The interest of these robust phosphanes as ligands was illustrated in palladium catalysis for the arylation of n-butyl furan with chloroarenes, using direct C-H activation of the heteroaromatic in the presence of low metal/ligand loadings (0.5-1.0 mol %). Thus, 4-chlorobenzonitrile, 4-chloronitrobenzene, 4-chloropropiophenone, and 4-(trifluoromethyl)chlorobenzene were efficiently coupled to n-butyl furan, using Pd(OAc)(2) associated to the new diphosphane ligands 1,1'-bis(diisopropylphosphanyl)-3,3'-di(triphenyl)methyl ferrocene (15) or 1,1'-bis(dicyclohexylphosphanyl)-3,3'-di(triphenyl)methylferrocene (16), which respectively hold the electron-rich -Pi-Pr(2) and -PCy(2) groups.

[Total analysis of organic rubber additives].

PubMed

He, Wen-Xuan; Robert, Shanks; You, Ye-Ming

2010-03-01

In the present paper, after middle pressure chromatograph separation using both positive phase and reversed-phase conditions, the organic additives in ethylene-propylene rubber were identified by infrared spectrometer. At the same time, by using solid phase extraction column to maintain the main component-fuel oil in organic additves to avoid its interfering with minor compounds, other organic additves were separated and analysed by GC/Ms. In addition, the remaining active compound such as benzoyl peroxide was identified by CC/Ms, through analyzing acetone extract directly. Using the above mentioned techniques, soften agents (fuel oil, plant oil and phthalte), curing agent (benzoylperoxide), vulcanizing accelerators (2-mercaptobenzothiazole, ethyl thiuram and butyl thiuram), and antiagers (2, 6-Di-tert-butyl-4-methyl phenol and styrenated phenol) in ethylene-propylene rubber were identified. Although the technique was established in ethylene-propylene rubber system, it can be used in other rubber system.

Formal [4+2] cycloaddition of di-tert-butyl 2-ethoxycyclobutane-1,1-dicarboxylate with ketones or aldehydes and tandem lactonization.

PubMed

Okado, Ryohei; Nowaki, Aya; Matsuo, Jun-Ichi; Ishibashi, Hiroyuki

2012-01-01

A catalytic amount of tin(IV) chloride catalyzed formal [4+2] cycloaddition reaction of di-tert-butyl 2-ethoxycyclobutane-1,1-carboxylate with ketones or aldehydes to give diethyl 6-ethoxydihydro-2H-pyran-3,3(4H)-dicarboxylates, whereas two equivalents of trimethylsilyl triflate promoted tandem [4+2] cycloaddition and lactonization to afford 3-oxo-2,6-dioxabicyclo[2.2.2]octane-4-carboxylate esters.

The tert-butyl cation on zeolite Y: A theoretical and experimental study

NASA Astrophysics Data System (ADS)

Rosenbach, Nilton, Jr.; dos Santos, Alex P. A.; Franco, Marcelo; Mota, Claudio J. A.

2010-01-01

The structure and energy of the tert-butyl cation on zeolite Y were calculated at ONIOM(MP2(FULL)/6-31G( d, p):MNDO) level. The results indicated that the tert-butyl cation is a minimum and lies between 40 and 51 kJ mol -1 above in energy to the tert-butoxide, depending on the level of calculation. Both species are stabilized through hydrogen bonding interactions with the framework oxygen atoms. Experimental data of nucleophilic substitution of tert-butylchloride and bromide over NaY impregnated with NaCl or NaBr give additional support for the formation of the tert-butyl cation as a discrete intermediate on zeolite Y, in agreement with the calculations.

Hydroalumination of a chlorotrialkynylsilane: spontaneous stepwise 1,3-dyotropic rearrangement via an intermediate silyl cation.

PubMed

Uhl, Werner; Bohnemann, Jörg; Layh, Marcus; Würthwein, Ernst-Ulrich

2014-07-07

A new functionalised alkynylsilane, Cl-Si(CC-CMe3 )3 (3), was obtained by a facile multistep synthesis. Treatment of 3 with equimolar quantities of the hydrides H-M(CMe3 )2 (M=Al, Ga) gave the mixed alkenyl-di(alkynyl)silanes, in which the chlorine atom adopts a bridging position between the aluminium and silicon atoms. Dual hydrogallation of 3 resulted in the formation of a di(alkenyl)-alkynylsilane containing two gallium atoms, one of which is coordinated to the chlorine atom, and the second is bonded to the α-carbon atom of the remaining alkynyl group. A tert-butylsilane was unexpectedly formed by a unique 1,3-dyotropic chlorine-tert-butyl exchange for the corresponding dialuminium compound. One aluminium atom is bonded to a tert-butyl group, a terminal chlorine atom and the α-carbon atom of the ethynyl moiety; the second is coordinatively unsaturated, with two terminal tert-butyl substituents. High-level quantum-chemical calculations favour a stepwise dyotropic rearrangement with an intermediate cationic silicon species over a simultaneous tert-butyl-chlorine migration via a five-coordinate silicon atom in the transition state. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photochemistry and photooxidation of tetraphenyl-p-dioxin

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

George, M.V.; Kumar, C.V.; Scaiano, J.C.

1979-09-20

Laser flash photolysis studies of tetraphenyl-p-dioxin have led to the characterization of its triplet state. The T-T absorption spectra shows maxima at 350 and 545 nm; the triplet has a lifetime of 535 ns in methanol and can be quenched by di-tert-butyl nitroxide, paraquat dications, oxygen, and di-tert-butyl selenoketone. The interaction of the triplet with oxygen leads to the formation of singlet oxygen which in turn reacts with the title compound to yield benzil.

Crystal structure of bis-[tetra-kis-(tetra-hydro-furan-κO)lithium] bis[μ-2,2',2''-methanetriyltris(4,6-di-tert-butylphenolato)-κ4O,O':O',O'']-dimagnesiate.

PubMed

Zhou, Hongyan; Wang, Lei

2017-07-01

The title ion-association metal complex, [Li(C 4 H 8 O) 4 ] 2 [Mg 2 (C 43 H 61 O 3 ) 2 ], has been synthesized from the tridentate phenolic ligand tris-(3,5-di- tert -butyl-2-hy-droxy-phen-yl)methane in tetra-hydro-furan (THF). The aryl-oxo magnesiate complex anion is binuclear with each Mg 2 O 4 complex unit inversion-related and bridged through the two tridentate chelating phenolate O-donors of the ligand. The complex centres have a distorted tetra-hedral stereochemistry [Mg-O range 1.8796 (17)-2.0005 (16) Å] and an Mg⋯Mg separation of 2.9430 (14) Å]. The LiO 4 coodination sphere of the cation comprises four THF O-donor atoms and has a slightly distorted tetra-hedral conformation [Li-O range 1.899 (5)- 1.953 (5) Å]. In the crystal, a number of stabilizing intra-anion C-H⋯O hydrogen-bonding inter-actions are present but no inter-species associations are found.

21 CFR 181.27 - Plasticizers.

Code of Federal Regulations, 2010 CFR

2010-04-01

...: Acetyl tributyl citrate. Acetyl triethyl citrate. p-tert-Butylphenyl salicylate. Butyl stearate. Butylphthalyl butyl glycolate. Dibutyl sebacate. Di-(2-ethylhexyl) phthalate (for foods of high water content...

21 CFR 181.27 - Plasticizers.

Code of Federal Regulations, 2011 CFR

2011-04-01

...: Acetyl tributyl citrate. Acetyl triethyl citrate. p-tert-Butylphenyl salicylate. Butyl stearate. Butylphthalyl butyl glycolate. Dibutyl sebacate. Di-(2-ethylhexyl) phthalate (for foods of high water content...

In vitro growth inhibition of mastitis causing bacteria by phenolics and metal chelators

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

Chew, B.P.; Tjoelker, L.W.; Tanaka, T.S.

1985-11-01

Antimicrobial activities of three phenolic compounds and four metal chelators were tested at 0, 250, 500, and 1000 ppm in vitro against four major mastitis-causing bacteria, Streptococcus agalactiae, Staphylococcus aureus, Klebsiella pnuemoniae, and Escherichia coli. Overall, butylated hydroxyanisole and tert-butylhydroquinone showed the greatest antimicrobial activity. These phenolics were bactericidal at 250 to 500 ppm against all four bacteria tested. The butylated hydroxytoluene was bactericidal against the gram-positive bacteria but was ineffective against the coliforms. At 250 ppm, disodium ethylenediaminetetraacetic acid was bactericidal against the gram-positive bacteria but much less effective against the gram-negatives. However, diethylene-triaminepentaacetic acid was more growth inhibitorymore » than ethylenediaminetetraacetic acid against the gram-negative bacteria and especially against Escherichia coli. All other compounds were generally much less effective or ineffective against all four microorganisms. Therefore, butylated hydroxyanisole, butylated hydroxytoluene, tert-butylhydroquinone, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid may have practical implications in the prevention or treatment of bovine mastitis.« less

Peripheral substitution of pheophorbides and bacteriopheophorbides to promote inclusion into inert carrier systems for PDT

NASA Astrophysics Data System (ADS)

Roehrs, Susanne; Ruebner-Heuermann, Anja; Hartwich, G.; Scheer, H.; Moser, Joerg G.

1996-01-01

Pheophorbide a ethyl ester, pyropheophorbide a ethyl ester, and bacteriopheophorbide ethyl ester were substituted in 31-position with tert.butyl phenoxy or tert.butyl benzoic acid ester groups resp. in order to enhance affinity to (beta) -cyclodextrin dimers which form inclusion complexes with these photosensitizing drugs. This is a first step to construct inert transport complexes in order to photosensitize specifically cancer cells.

Photo-inducible cytotoxic and clastogenic activities of 3,6-di-substituted acridines obtained by acylation of proflavine.

PubMed

Benchabane, Yohann; Di Giorgio, Carole; Boyer, Gérard; Sabatier, Anne-Sophie; Allegro, Diane; Peyrot, Vincent; De Méo, Michel

2009-06-01

The cytotoxicity and photo-enhanced cytotoxicity of a series of 18 3,6-di-substituted acridines were evaluated on both tumour CHO cells and human normal keratinocytes, and compared to their corresponding clastogenicity as assessed by the micronucleus assay. Compounds 2f tert-butyl N-[(6-tert-butoxycarbonylamino)acridin-3-yl]carbamate and 2d N-[6-(pivalamino)acridin-3-yl]pivalamide displayed a specific cytotoxicity on CHO cells. These results suggested that the two derivatives could be considered as interesting candidates for anticancer chemotherapy and hypothesized that the presence of 1,1-dimethylethyl substituents was responsible for a strong nonclastogenic cytotoxicity. Compounds 2b and 2c, on the contrary, displayed a strong clastogenicity. They indicated that the presence of nonbranched aliphatic chains on positions 3 and 6 of the acridine rings tended to induce a significant clastogenic effect. Finally, they established that most of the acridine compounds could be photo-activated by UVA-visible rays and focussed on the significant role of light irradiation on their biological properties.

Mono-, di-, and tri- tert-butyl ethers of glycerol . A molecular spectroscopic study

NASA Astrophysics Data System (ADS)

Jamróz, Małgorzata E.; Jarosz, Małgorzata; Witowska-Jarosz, Janina; Bednarek, Elżbieta; Tęcza, Witold; Jamróz, Michał H.; Dobrowolski, Jan Cz.; Kijeński, Jacek

2007-07-01

MS, NMR, IR and Raman molecular spectroscopy techniques were applied to characterize 3- tert-butoxy-propane-1,2-diol, 1,3-di- tert-butoxy-propan-2-ol, and 1,2,3-tri- tert-butoxy-propane. These ethers are the main products of glycerol etherification reaction and are excellent oxygen additives for diesel fuel. Computational DFT/ B3LYP/6-31G ** studies were performed to support and rationalize both vibrational spectroscopy analysis and the isomer ratio.

Demethylation of 5,n-di-tert-butyl-8,n-dimethoxy[2.n]metacyclophane-1-ynes with BBr3 to afford novel [n]benzofuranophanes

NASA Astrophysics Data System (ADS)

Akther, Thamina; Islam, Md Monarul; Matsumoto, Taisuke; Tanaka, Junji; Feng, Xing; Redshaw, Carl; Yamato, Takehiko

2016-10-01

Novel [n]benzofuranophanes (n = 8 & 10) 2a-b have been prepared by successive intramolecular cyclization from 5,19-di-tert-butyl-8,22-dimethoxy[n]metacyclophane-1-yne (syn-1a-b) by treatment with BBr3 in CH2Cl2 at room temperature for 8h. [2.n]Benzofuranophanes 2a-b were also obtained by treatment of 1,2-di-endo-bromo-5,19-di-tert-butyl-8,22-dimethoxy[n]metacyclophane (meso-3a-b) with BBr3 in CH2Cl2 by using the same reaction conditions. 1H NMR spectra of 2a-b reveals the formation of intramolecular hydrogen bonding between hydroxyl proton with the oxygen of the furan moiety and X-ray analysis shows that the lengths between H (OH) and O (furan) are 1.981 and 1.823 Å̊, respectively. The conformation of [8]benzofuranophane 2a in solution is rigid with restricted rotation around the diaryl linkage rather than [10]benzofuranophane 2b because of weak intramolecular hydrogen bonding and the short length of the cross-linking chain.

Use B-spline interpolation fitting baseline for low concentration 2, 6-di-tertbutyl p-cresol determination in jet fuels by differential pulse voltammetry

NASA Astrophysics Data System (ADS)

Wen, D. S.; Wen, H.; Shi, Y. G.; Su, B.; Li, Z. C.; Fan, G. Z.

2018-01-01

The B-spline interpolation fitting baseline in electrochemical analysis by differential pulse voltammetry was established for determining the lower concentration 2,6-di-tert-butyl p-cresol(BHT) in Jet Fuel that was less than 5.0 mg/L in the condition of the presence of the 6-tert-butyl-2,4-xylenol.The experimental results has shown that the relative errors are less than 2.22%, the sum of standard deviations less than 0.134mg/L, the correlation coefficient more than 0.9851. If the 2,6-ditert-butyl p-cresol concentration is higher than 5.0mg/L, linear fitting baseline method would be more applicable and simpler.

Synthesis and structural characterization of lithium, sodium and potassium complexes supported by a tridentate amino-bisphenolate ligand

NASA Astrophysics Data System (ADS)

Durango-García, Clara J.; Rufino-Felipe, Ernesto; López-Cardoso, Marcela; Muñoz-Hernández, Miguel-Ángel; Montiel-Palma, Virginia

2018-07-01

Reactions of methylamino-N,N-bis(2-methylene-4,6-di-tert-butylphenol) (1) with one or two equivalents of bulk Li, Na or K metals in THF or DMSO render mono or dialkali metal complexes depending on the stoichiometric ratio of the reactants. The metal-methylamino-N-(2-methylene-4,6-tert-butylphenol)sbnd N-(2-methylene-4,6-tert-butylphenolate) complexes, 2Li, 2Na and 2K, are generated upon the substitution of a single phenol hydrogen of 1. In the solid state, complex 2Na is a dimer due to the establishment of two symmetric hydrogen bonds between two adjacent molecules. The Na center also engages into the formation of a ten-membered metallacycle ring with a butterfly-like structure. Due to dimerization, an intermolecular six-membered core is formed involving two sodium and four oxygen atoms. The weakly coordinated nitrogen atom from the ligand is nearly perpendicular to the hexagonal core. The dimetal-methylamino-N,N‧-bis(2-methylene-4,6-di-tert-butylphenolate) complexes, 3Li, 3Na and 3K result from metal substitution of the two phenol hydrogens from ligand 1. The SC-XRD structures of 3Li and 3Na are discreet, each incorporating two metal atoms in different coordination environments. Ten-membered rings with boat-boat conformations are also observed as are rhombic central M2O2 cores. The molecular structure of 3K in DMSO shows a higher degree of aggregation. It effectively comprises four K atoms, two ligand backbones and seven solvent molecules forming a central four-membered K2O2 ring perpendicular to an eight-membered structure formed also by K and O atoms spanning over the two ligand moieties.

Catalytic performance of strong acid catalyst: Methyl modified SBA-15 loaded perfluorinated sulfonic acid obtained by the waste perfluorinated sulfonic acid ion exchange membrane

NASA Astrophysics Data System (ADS)

Jiang, Tingshun; Huang, Qiuyan; Li, Yingying; Fang, Minglan; Zhao, Qian

2018-02-01

Mesoporous molecular sieve (SBA-15) was modified using the trimethylchlorosilane as functional agent and the silylation SBA-15 mesoporous material was prepared in this work. The alcohol solution of perfluorinated sulfonic acid dissolved from the waste perfluorinated sulfonic acid ion exchange membrane (PFSIEM) was loaded onto the resulting mesoporous material by the impregnation method and their physicochemical properties were characterized by FT-IR, N2-physisorption, XRD, TG-DSC and TEM. The catalytic activities of these synthesized solid acid catalysts were evaluated by alkylation of phenol with tert-butyl alcohol. The influence of reaction temperature, weight hour space velocity (WHSV) and reaction time on the phenol conversion and product selectivity were assessed by means of a series of experiments. The results showed that with the increase of the active component of the catalyst, these catalysts still remained good mesoporous structure, but the mesoporous ordering decreased to some extent. These catalysts exhibited good catalytic performance for the alkylation of phenol with tert-butanol. The maximum phenol conversion of 89.3% with 70.9% selectivity to 4-t-butyl phenol (4-TBP) was achieved at 120 °C and the WHSV is 4 h-1. The methyl group was loaded on the surface of the catalyst by trimethylchlorosilane. This is beneficial to retard the deactivation of the catalyst. In this work, the alkylation of phenol with tert-butyl alcohol were carried out using the methyl modified SBA-15 mesoporous materials loaded perfluorinated sulfonic acid as catalysts. The results show that the resulting catalyst exhibited high catalytic activity.

40 CFR 464.31 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (dichloromethane) 55. naphthalene 64. pentachlorophenol 65. phenol 66. bis(2-ethylhexyl)phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72. benzo (a)anthracene (1,2...-ethylhexyl) phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 72. benzo (a)anthracene (1,2...

40 CFR 433.11 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

...-propylamine Pentachlorophenol Phenol Bis (2-ethylhexyl) phthalate Butyl benzyl phthalate Di-n-butyl phthalate Di-n-octyl phthalate Diethyl phthalate Dimethyl phthalate 1,2-Benzanthracene (benzo(a)anthracene...

40 CFR 433.11 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

...-propylamine Pentachlorophenol Phenol Bis (2-ethylhexyl) phthalate Butyl benzyl phthalate Di-n-butyl phthalate Di-n-octyl phthalate Diethyl phthalate Dimethyl phthalate 1,2-Benzanthracene (benzo(a)anthracene...

40 CFR 433.11 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

...-propylamine Pentachlorophenol Phenol Bis (2-ethylhexyl) phthalate Butyl benzyl phthalate Di-n-butyl phthalate Di-n-octyl phthalate Diethyl phthalate Dimethyl phthalate 1,2-Benzanthracene (benzo(a)anthracene...

In vitro and in vivo antibiofilm potential of 2,4-Di-tert-butylphenol from seaweed surface associated bacterium Bacillus subtilis against group A streptococcus.

PubMed

Viszwapriya, Dharmaprakash; Prithika, Udayakumar; Deebika, Sundaresan; Balamurugan, Krishnaswamy; Pandian, Shunmugiah Karutha

2016-10-01

Biofilm formation of Group A Streptococcus (GAS) is recognized as an important virulent determinant. The present study reports the antibiofilm potential of seaweed (Gracilaria gracilis) surface associated Bacillus subtilis against GAS. Purification revealed 2,4-Di-tert-butyl-phenol (DTBP) as the active principle. DTBP exhibited a dose dependent antibiofilm activity against GAS (SF370 & six different clinical M serotypes). Microscopic analysis revealed changes in cell surface architecture and reduced thickness upon DTBP treatment. Results of extracellular polymeric substance quantification, microbial adhesion to hydrocarbon assay and fourier transform infrared spectroscopic analysis suggested that DTBP probably interferes with the initial adhesion stage of biofilm formation cascade. Reduction in hyaluronic acid synthesis goes in unison with blood survival assay wherein, increased susceptibility to phagocytosis was observed. In vivo studies using Caenorhabditis elegans manifested the reduction in adherence and virulence, which prompts further investigation of the potential of DTBP for the treatment of GAS infections. Copyright © 2016 Elsevier GmbH. All rights reserved.

40 CFR 413.02 - General definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

...-nitrosodiphenylamine N-nitrosodi-n-propylamine Pentachlorophenol Phenol Bis (2-ethylhexyl) phthalate Butyl benzyl phthalate Di-n-butyl phthalate Di-n-octyl phthalate Diethyl phthalate Dimethyl phthalate 1,2-benzanthracene...

40 CFR 413.02 - General definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

...-nitrosodiphenylamine N-nitrosodi-n-propylamine Pentachlorophenol Phenol Bis (2-ethylhexyl) phthalate Butyl benzyl phthalate Di-n-butyl phthalate Di-n-octyl phthalate Diethyl phthalate Dimethyl phthalate 1,2-benzanthracene...

Influence of thermocleavable functionality on organic field-effect transistor performance of small molecules

NASA Astrophysics Data System (ADS)

Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar; Venugopalan, Vijay

2017-06-01

Diketopyrrolopyrrole based donor-acceptor-donor conjugated small molecules using ethylene dioxythiophene as a donor was synthesized. Electron deficient diketopyrrolopyrrole unit was substituted with thermocleavable (tert-butyl acetate) side chains. The thermal treatment of the molecules at 160 °C eliminated the tert-butyl ester group results in the formation of corresponding acid. Optical and theoretical studies revealed that the molecules adopted a change in molecular arrangement after thermolysis. The conjugated small molecules possessed p-channel charge transport characteristics in organic field effect transistors. The charge carrier mobility was increased after thermolysis of tert-butyl ester group to 5.07 × 10-5 cm2/V s.

Di-tert-butyl-chlorido(N,N-dibenzyl-dithio-carbamato)tin(IV).

PubMed

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R T

2011-02-26

The Sn(IV) atom in the title diorganotin dithio-carbamate, [Sn(C(4)H(9))(2)(C(15)H(14)NS(2))Cl], is penta-coordinated by an asymmetrically coordinating dithio-carbamate ligand, a Cl atom and two C atoms of the Sn-bound tert-butyl groups. The resulting C(2)ClS(2) donor set defines a coordination geometry inter-mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former.

Phenyl 3,5-di-tert-butyl-2-hy­droxy­benzoate

PubMed Central

Carreño, Alexander; Preite, Marcelo; Manriquez, Juan Manuel; Vega, Andrés; Chavez, Ivonne

2010-01-01

The title mol­ecule, C21H26O3, has a six-membered planar carbon ring as the central core, substituted at position 1 with phen­oxy­carbonyl, at position 2 with hy­droxy and at positions 3 and 5 with tert-butyl groups. The structure shows two independent but very similar mol­ecules within the asymmetric unit. For both independent mol­ecules, the ester carboxyl­ate group is coplanar with the central core, as reflected by the small C—C—O—C torsion angles [179.95 (17) and 173.70 (17)°]. In contrast, the phenyl substituent is almost perpendicular to the carboxyl­ate –CO2 fragment, as reflected by C—O—C—C torsion angles, ranging from 74 to 80°. The coplanarity between the central aromatic ring and the ester carboxyl­ate –CO2– group allows the formation of an intra­molecular hydrogen bond, with O⋯O distances of 2.563 (2) and 2.604 (2) Å. PMID:21589569

Kinetics and structure-activity relationship of dendritic bridged hindered phenol antioxidants to protect styrene against free radical induced peroxidation

NASA Astrophysics Data System (ADS)

Li, Cui-Qin; Guo, Su-Yue; Wang, Jun; Shi, Wei-Guang; Zhang, Zhi-Qiu; Wang, Peng-Xiang

2017-12-01

A series of dendritic poly(amido-amine) (PAMAM) bridged hindered phenols antioxidants were synthesized. The active antioxidant group (3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionic acid) was attached to two generations of PAMAM dendrimers, and their structure was verified by nuclear magnetic resonance (NMR) and fourier transform infrared spectra (FT-IR). The antioxidant abilities of the dendritic phenols to inhibit the oxidation of styrene were evaluated and the relationships between the length of core, the generation of dendrimers and the antioxidant activities were established. The reaction kinetics of scavenging peroxyl radicals was followed by oxygen consumption. The inhibition time ( t inh) values showed the dendritic phenols had the ability of scavenging peroxyl radicals, and that the antioxidant ability increased with the increasing length of the core and the generation. The kinetic analysis demonstrated that dendritic phenols could slow the rate of styrene peroxidation induced by AIBN, as shown by the number of trapping ROO· ( n), and this role was in accordance with that of the t inh values.

Boosting effect of ortho-propenyl substituent on the antioxidant activity of natural phenols.

PubMed

Marteau, Clémentine; Guitard, Romain; Penverne, Christophe; Favier, Dominique; Nardello-Rataj, Véronique; Aubry, Jean-Marie

2016-04-01

Seven new antioxidants derived from natural or synthetic phenols have been designed as alternatives to BHT and BHA antioxidants. Influence of various substituents at the ortho, meta and para positions of the aromatic core of phenols on the bond dissociation enthalpy of the ArO-H bond was evaluated using a DFT method B3LYP/6-311++G(2d,2p)//B3LYP/6-311G(d,p). This prediction highlighted the ortho-propenyl group as the best substituent to decrease the bond dissociation enthalpy (BDE) value. The rate constants of hydrogen transfer from these phenols to DPPH radical in a non-polar and non-protic solvent have been measured and were found to be in agreement with the BDE calculations. For o-propenyl derivatives from 2-tert-butyl-4-methylphenol, BHA, creosol, isoeugenol and di-o-propenyl p-cresol, fewer radicals were trapped by a single phenol molecule, i.e. a lower stoichiometric number. Reaction mechanisms involving the evolution of the primary phenoxyl radical ArO are proposed to rationalise these effects. Copyright © 2015 Elsevier Ltd. All rights reserved.

Growth Inhibition and DNA Damage Induced by X-Phenols in Yeast: A Quantitative Structure–Activity Relationship Study

PubMed Central

2017-01-01

Phenolic compounds and their derivatives are ubiquitous constituents of numerous synthetic and natural chemicals that exist in the environment. Their toxicity is mostly attributed to their hydrophobicity and/or the formation of free radicals. In a continuation of the study of phenolic toxicity in a systematic manner, we have examined the biological responses of Saccharomyces cerevisiae to a series of mostly monosubstituted phenols utilizing a quantitative structure–activity relationship (QSAR) approach. The biological end points included a growth assay that determines the levels of growth inhibition induced by the phenols as well as a yeast deletion (DEL) assay that assesses the ability of X-phenols to induce DNA damage or DNA breaks. The QSAR analysis of cell growth patterns determined by IC50 and IC80 values indicates that toxicity is delineated by a hydrophobic, parabolic model. The DEL assay was then utilized to detect genomic deletions in yeast. The increase in the genotoxicity was enhanced by the electrophilicity of the phenolic substituents that were strong electron donors as well as by minimal hydrophobicity. The electrophilicities are represented by Brown’s sigma plus values that are a variant of the Hammett sigma constants. A few mutant strains of genes involved in DNA repair were separately exposed to 2,6-di-tert-butyl-4-methyl-phenol (BHT) and butylated hydroxy anisole (BHA). They were subsequently screened for growth phenotypes. BHA-induced growth defects in most of the DNA repair null mutant strains, whereas BHT was unresponsive. PMID:29302629

Reaction of singlet-excited 2,3-diazabicyclo[2.2.2]oct-2-ene and tert-butoxyl radicals with aryl-substituted benzofuranones.

PubMed

Lundgren, Cecilia Vannesjö; Koner, Apurba L; Tinkl, Michael; Pischel, Uwe; Nau, Werner M

2006-03-03

5,7-Di-tert-butyl-3-aryl-3H-benzofuran-2-ones are lactones with potential antioxidant activity, owing to their abstractable benzylic C-H hydrogens. The fluorescence quenching of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO), an established probe for the hydrogen-donor propensity of chain-breaking antioxidants, was investigated for 16 aryl-substituted benzofuranone derivatives [m,m-(CF3)2, p-CN, m-CN, p-CF3, p-COOCH3, m-CF3, p-Cl, p-F, H, m-CH3, p-CH3, m,p-(CH3)2, p-OCH3, o-CH3, o-CF3, o,m-(CH3)2]. Analysis of the rate data in terms of a linear free energy relationship yielded a reaction constant of rho = +0.35. This implies that n,pi*-excited DBO acts as nucleophilic species. In contrast, hydrogen abstraction of tert-butoxyl radicals from the benzofuranones was accelerated by electron-donating substituents (rho = -0.23), in conformity with the electrophilic character of oxygen-centered alkoxyl radicals. Possible implications for the optimization of the hydrogen-donor propensity of antioxidants through structural variation are discussed.

Disposition of 2,6-di-tert-butyl-4-nitrophenol (DBNP), a submarine atmosphere contaminant, in male Sprague-Dawley rats.

PubMed

Still, Kenneth R; Jung, Anne E; Ritchie, Glenn D; Jederberg, Warren W; Wilfong, Erin R; Briggs, G Bruce; Arfsten, Darryl P

2005-07-01

The phenol 2,6-di-tert-butyl-4-nitrophenol (DBNP) is a contaminant found onboard submarines and is formed by the nitration of an antioxidant present in turbine lubricating oil TEP 2190. DBNP has been found on submarine interior surfaces, on eating utensils and dishes, and on the skin of submariners. DBNP exposure is a potential health concern because it is an uncoupler of mitochondrial oxidative phosphorylation. Adult male rats were dosed once by oral gavage with 15 or 40 mg/kg DBNP mixed with 14C-DBNP in kanola oil and 0.8% v/v DMSO (n = 16/group). The distribution of 14C in major tissues was measured over time for up to 240 h post-dose. Unexpectedly, 6/16 (40%) of the rats gavaged with 40 mg/kg DBNP died within 24 h of dosing. Prostration, no auditory startle response, reduced locomotor activity, and muscular rigidity persisted in survivors for up to 8 days after dosing. For animals dosed with 15 mg/kg DBNP, radioactivity levels were significantly elevated in the following tissues 24h after dosing: fat>liver>kidneys>heart>lungs>brain>striated muscle>spleen. Radioactivity levels were elevated for fat, liver, kidney, heart, and lungs of animals euthanized 144 h post-dosing and in the liver of animals euthanized 240 h post-dosing. These findings suggest that DBNP may accumulate in the body as a result of continuous or repeat exposures of short interval to DBNP.

Di-tert-butyl­chlorido(N,N-dibenzyl­dithio­carbamato)tin(IV)

PubMed Central

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R. T.

2011-01-01

The SnIV atom in the title diorganotin dithio­carbamate, [Sn(C4H9)2(C15H14NS2)Cl], is penta­coordinated by an asymmetrically coordinating dithio­carbamate ligand, a Cl atom and two C atoms of the Sn-bound tert-butyl groups. The resulting C2ClS2 donor set defines a coordination geometry inter­mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. PMID:21522304

40 CFR Appendix A to Part 423 - 126 Priority Pollutants

Code of Federal Regulations, 2012 CFR

2012-07-01

...-propylamin 064Pentachlorophenol 065Phenol 066Bis(2-ethylhexyl) phthalate 067Butyl benzyl phthalate 068Di-N-Butyl Phthalate 069Di-n-octyl phthalate 070Diethyl Phthalate 071Dimethyl phthalate 0721,2-benzanthracene...

40 CFR Appendix A to Part 423 - 126 Priority Pollutants

Code of Federal Regulations, 2014 CFR

2014-07-01

...-propylamin 064Pentachlorophenol 065Phenol 066Bis(2-ethylhexyl) phthalate 067Butyl benzyl phthalate 068Di-N-Butyl Phthalate 069Di-n-octyl phthalate 070Diethyl Phthalate 071Dimethyl phthalate 0721,2-benzanthracene...

40 CFR Appendix A to Part 423 - 126 Priority Pollutants

Code of Federal Regulations, 2010 CFR

2010-07-01

...-propylamin 064Pentachlorophenol 065Phenol 066Bis(2-ethylhexyl) phthalate 067Butyl benzyl phthalate 068Di-N-Butyl Phthalate 069Di-n-octyl phthalate 070Diethyl Phthalate 071Dimethyl phthalate 0721,2-benzanthracene...

40 CFR Appendix A to Part 423 - 126 Priority Pollutants

Code of Federal Regulations, 2011 CFR

2011-07-01

...-propylamin 064Pentachlorophenol 065Phenol 066Bis(2-ethylhexyl) phthalate 067Butyl benzyl phthalate 068Di-N-Butyl Phthalate 069Di-n-octyl phthalate 070Diethyl Phthalate 071Dimethyl phthalate 0721,2-benzanthracene...

Effects of hydroxylated benzaldehyde derivatives on radiation-induced reactions involving various organic radicals

NASA Astrophysics Data System (ADS)

Ksendzova, G. A.; Samovich, S. N.; Sorokin, V. L.; Shadyro, O. I.

2018-05-01

In the present paper, the effects of hydroxylated benzaldehyde derivatives and gossypol - the known natural occurring compound - on formation of decomposition products resulting from radiolysis of ethanol and hexane in deaerated and oxygenated solutions were studied. The obtained data enabled the authors to make conclusions about the effects produced by the structure of the compounds under study on their reactivity towards oxygen- and carbon-centered radicals. It has been found that 2,3-dihydroxybenzaldehyde, 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde and 4,6-di-tert-butyl-3-(1,3-dioxane-2-yl)-1,2-dihydroxybenzene are not inferior in efficiency to butylated hydroxytoluene - the industrial antioxidant - as regards suppression of the radiation-induced oxidation processes occurring in hexane. The derivatives of hydroxylated benzaldehydes were shown to have a significant influence on radiation-induced reactions involving α-hydroxyalkyl radicals.

(E)-2′-[(3,5-Di-tert-butyl-2-hy­droxy­benzyl­idene)amino]-1,1′-binaphthalen-2-ol methanol monosolvate

PubMed Central

He, Dian; Li, Chong; Wang, Xiaohong

2011-01-01

The title compound, C35H35NO2·CH4O, was obtained by the reaction of rac-2-amino-2-hy­droxy-1,1-binaphthyl and 3,5-di-tert-butyl-2-hy­droxy­benzaldehyde in absolute methanol. In the Schiff base mol­ecule, the two naphthyl bicycles are twisted by 71.15 (5)°. One hy­droxy group is involved in intra­molecular O—H⋯N hydrogen bond, while the methanol solvent mol­ecule is linked to another hy­droxy group via an inter­molecular O—H⋯O hydrogen bond. PMID:22219946

Adduction of DNA with MTBE and TBA in mice studied by accelerator mass spectrometry.

PubMed

Yuan, Y; Wang, H F; Sun, H F; Du, H F; Xu, L H; Liu, Y F; Ding, X F; Fu, D P; Liu, K X

2007-12-01

Methyl tert-butyl ether (MTBE) is a currently worldwide used octane enhancer substituting for lead alkyls and gasoline oxygenate. Our previous study using doubly (14)C-labeled MTBE [(CH(3))(3) (14)CO(14)CH(3)] has shown that MTBE binds DNA to form DNA adducts at low dose levels in mice. To elucidate the mechanism of the binding reaction, in this study, the DNA adducts with singly (14)C-labeled MTBE, which was synthesized from (14)C-methanol and tert-butyl alcohol (TBA), or (14)C-labeled TBA in mice have been measured by ultra sensitive accelerator mass spectrometry. The results show that the methyl group of MTBE and tert-butyl alcohol definitely form adducts with DNA in mouse liver, lung, and kidney. The methyl group of MTBE is the predominant binding part in liver, while the methyl group and the tert-butyl group give comparable contributions to the adduct formation in lung and kidney.

Effects of intraperitoneal administration of the GABAB receptor positive allosteric modulator 2,6-di tert-butyl-4-(2-hydroxy-2,2-dimethyl-propyl)-phenol (CGP7930) on food intake in non-deprived rats.

PubMed

Ebenezer, Ivor S

2012-09-05

γ-Aminobutyric acid-(B) (GABA(B)) receptor positive allosteric modulators (PAMs) act on an allosteric site on the GABA(B) receptor to potentiate the effects of GABA and GABA(B) receptor agonists. It has previously been demonstrated that the GABA(B) receptor agonist baclofen increases food intake in non-deprived rats. The aim of this study was to investigate whether the GABA(B) receptor PAM 2,6-di tert-butyl-4-(2-hydroxy-2,2-dimethyl-propyl)-phenol (CGP7930) would (i) increase food intake, and (ii) potentiate the hyperphagic effects of baclofen in rats. In Experiment 1, the effects of intraperitoneal (i.p.) administration of CGP7930 (1, 6 and 12 mg/kg) was investigated on food intake in non-deprived male Wistar rats. The 12 mg/kg dose of CGP7930 significantly increased cumulative food intake 30, 60 and 120 min (P<0.05, in each case) after administration. The 1 and 6 mg/kg doses were without effect. In Experiment 2, the effects of pretreatment with CGP7930 (6 mg/kg; i.p.) 5 min prior to administration of baclofen (2mg/kg, i.p.) was investigated on 30min cumulative food intake in non-deprived male Wistar rats. Baclofen (2mg/kg) significantly increased food intake compared with vehicle treatment (P<0.01). CGP7930 (6 mg/kg) had no effect on feeding. However, pretreatment with CGP7930 (6 mg/kg) significantly potentiated the hyperphagic effects of baclofen (2mg/kg) (P<0.01). These findings show that CGP7930 increases food intake and enhances the hyperphagic effects of baclofen, and are consistent with in vitro studies that suggest that it potentiates the effects of endogenous GABA and GABA(B) receptor agonists by allosteric modulation of the GABA(B) receptor. Copyright © 2012 Elsevier B.V. All rights reserved.

(N-Benzyl-N-ethyl-dithio-carbamato)di-tert-butyl-chloridotin(IV).

PubMed

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R T

2011-02-26

The Sn(IV) atom in the title diorganotin dithio-carbamate, [Sn(C(4)H(9))(2)Cl(C(10)H(12)NS(2))], is penta-coordinated by an asymmetrically coordinating dithio-carbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups. The resulting C(2)ClS(2) donor set defines a coordination geometry inter-mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. In the crystal structure, C-H⋯π contacts link centrosymmetrically related mol-ecules into dimeric aggregates.

Anaerobic biodegradability of alkylphenols and fuel oxygenates in the presence of alternative electron acceptors.

PubMed

Puig-Grajales, L; Tan, N G; van der Zee, F; Razo-Flores, E; Field, J A

2000-11-01

Alkylphenols and fuel oxygenates are important environmental pollutants produced by the petrochemical industry. A batch biodegradability test was conducted with selected ortho-substituted alkylphenols (2-cresol, 2,6-dimethylphenol and 2-ethylphenol), fuel oxygenates (methyl tert-butyl ether, ethyl tert-butyl ether and tert-amylmethyl ether) and tert-butyl alcohol (TBA) as model compounds. The ortho-substituted alkylphenols were not biodegraded after 100 days of incubation under methanogenic, sulfate-, or nitrate-reducing conditions. However, biodegradation of 2-cresol and 2-ethylphenol (150 mg l(-1)) was observed in the presence of Mn (IV) as electron acceptor. The biodegradation of these two compounds took place in less than 15 days and more than 90% removal was observed for both compounds. Mineralization was indicated since no UV-absorbing metabolites accumulated after 23 days of incubation. These alkylphenols were also slowly chemically oxidized by Mn (IV). No biodegradation of fuel oxygenates or TBA (1 g l(-1)) was observed after 80 or more days of incubation under methanogenic, Fe (III)-, or Mn (IV)-reducing conditions, suggesting that these compounds are recalcitrant under anaerobic conditions. The fuel oxygenates caused no toxicity towards acetoclastic methanogens activity in anaerobic granular sludge.

21 CFR 177.2470 - Polyoxymethylene copolymer.

Code of Federal Regulations, 2013 CFR

2013-04-01

... its production. The quantity of any optional adjuvant substance employed in the production of the.... Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane. (2) Lubricant: N,N...

21 CFR 177.2470 - Polyoxymethylene copolymer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... its production. The quantity of any optional adjuvant substance employed in the production of the.... Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane. (2) Lubricant: N,N...

21 CFR 177.2470 - Polyoxymethylene copolymer.

Code of Federal Regulations, 2010 CFR

2010-04-01

... its production. The quantity of any optional adjuvant substance employed in the production of the.... Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane. (2) Lubricant: N,N...

21 CFR 177.2470 - Polyoxymethylene copolymer.

Code of Federal Regulations, 2012 CFR

2012-04-01

... its production. The quantity of any optional adjuvant substance employed in the production of the.... Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane. (2) Lubricant: N,N...

Reactivities of Substituted α-Phenyl-N-tert-butyl Nitrones

PubMed Central

2015-01-01

In this work, a series of α-phenyl-N-tert-butyl nitrones bearing one, two, or three substituents on the tert-butyl group was synthesized. Cyclic voltammetry (CV) was used to investigate their electrochemical properties and showed a more pronounced substituent effect for oxidation than for reduction. Rate constants of superoxide radical (O2•–) reactions with nitrones were determined using a UV–vis stopped-flow method, and phenyl radical (Ph•) trapping rate constants were measured by EPR spectroscopy. The effect of N-tert-butyl substitution on the charge density and electron density localization of the nitronyl carbon as well as on the free energies of nitrone reactivity with O2•– and HO2• were computationally rationalized at the PCM/B3LYP/6-31+G**//B3LYP/6-31G* level of theory. Theoretical and experimental data showed that the rates of the reaction correlate with the nitronyl carbon charge density, suggesting a nucleophilic nature of O2•– and Ph• addition to the nitronyl carbon atom. Finally, the substituent effect was investigated in cell cultures exposed to hydrogen peroxide and a correlation between the cell viability and the oxidation potential of the nitrones was observed. Through a combination of computational methodologies and experimental methods, new insights into the reactivity of free radicals with nitrone derivatives have been proposed. PMID:24968285

Asymmetric epoxidation of unsaturated ketones catalyzed by heterobimetallic rare earth-lithium complexes bearing phenoxy-functionalized chiral diphenylprolinolate ligand.

PubMed

Qian, Qinqin; Tan, Yufang; Zhao, Bei; Feng, Tao; Shen, Qi; Yao, Yingming

2014-09-05

Four novel heterobimetallic complexes [REL2]{[(THF)3Li]2(μ-Cl)} stabilized by chiral phenoxy-functionalized prolinolate (RE = Yb (1), Y (2), Sm (3), Nd (4), H2L = (S)-2,4-di-tert-butyl-6-[[2-(hydroxydiphenylmethyl)pyrrolidin-1-yl]methyl]phenol have been synthesized and characterized. These readily available complexes are highly active in catalyzing the epoxidation of α,β-unsaturated ketones, while the enantioselectivity varies according to the ionic radii of the rare earth center. A series of chalcone derivatives were converted to chiral epoxides in 80 → 99% ee at 0 °C using TBHP as the oxidant in the presence of 10 mol % of 1.

Alkylation of phenol by alcohols in the presence of aluminum phenolate

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

Koshchii, V.A.; Kozlikovskii, Ya.B.; Matyusha, A.A.

1988-12-20

The reaction of phenol with alcohols in the presence of aluminum phenolate leads to a mixture of 2- and 4-alkylphenols, of which the former predominate in the case of benzyl, tert-butyl, and cyclohexyl alcohols, and the latter in the case of dimethylphenyl- and diphenylmethylcarbinols. Only triphenyl(4-hydroxyphenyl)-methane is formed during the alkylation of phenol by triphenylcarbinol. In individual experiments the formation of small amounts of alkyl phenyl ethers and 2,6-dialkylphenols was observed.

Novel non-symmetrical bifunctionally-substituted phthalonitriles and corresponding d-metal phthalocyaninates

NASA Astrophysics Data System (ADS)

Vashurin, Artur; Maizlish, Vladimir; Tikhomirova, Tatiyana; Nemtseva, Marina; Znoyko, Serafima; Aleksandriiskii, Viktor

2018-05-01

The work reports synthesis of 4-(2-tert-butyl-4,5-dicyanophenylsulfonyl)benzene and its analogue containing carboxyl group in phenyl fragment by nucleophilic substitution of nitro-group of 4-tert-butyl-5-nitrophthalonitrile. Unique structure of the obtained compounds is explained by presence of bulky tert-butyl substituent in combination with carboxyl group, which being part of phthalocyanine molecule impart it higher solubility within different solvents (organic and water mediums) and act as anchoring groups. Based on obtained nitriles phthalocyanine complexes of copper, nickel, cobalt and magnesium are synthesized with good yields. Demetallization of initial magnesium phthalocyanine by hydrochloric acid was performed in order to obtain ligand of phthalocyanine. Synthetic and purification techniques are described in detail. Obtained substances are of specific structure making them to be applied in sensorics for smart materials production, as sensitizers or part of molecular magnets. The structure, NMR and IR spectra are modeled using special software. Resulting experimental and theoretical data are compared. The results show sufficient correlation that confirms correctness of chosen methods and its applicability for theoretical studying compounds related to investigated ones.

A radical pathway in catecholase activity with nickel(II) complexes of phenol based "end-off" compartmental ligands.

PubMed

Ghosh, Totan; Adhikary, Jaydeep; Chakraborty, Prateeti; Sukul, Pradip K; Jana, Mahendra Sekhar; Mondal, Tapan Kumar; Zangrando, Ennio; Das, Debasis

2014-01-14

Seven dinuclear and one dinuclear based dicyanamide bridged polymeric Ni(II) complexes of phenol based compartmental ligands (HL(1)-HL(4)) have been synthesized with the aim to investigate their catecholase-like activity and to evaluate the most probable mechanistic pathway involved in this process. The complexes have been characterized by routine physicochemical studies as well as by X-ray single crystal structure analyses namely [Ni2(L(2))(SCN)3(H2O)(CH3OH)] (), [Ni2(L(4))(SCN)3(CH3OH)2] (), [Ni2(L(2))(SCN)2(AcO)(H2O)] (), [Ni2(L(4))(SCN)(AcO)2] (), [Ni2(L(2))(N3)3(H2O)2] (), [Ni2(L(4))(N3)3(H2O)2] (), [Ni2(L(1))(AcO)2(N(CN)2)]n () and [Ni2(L(3))(AcO)2(N(CN)2)] (), [SCN = isothiocyanate, AcO = acetate, N3 = azide, and N(CN)2 = dicyanamide anion; L(1-4) = 2,6-bis(R2-iminomethyl)-4-R1-phenolato, where R1 = methyl and tert-butyl, R2 = N,N-dimethyl ethylene for L(1-2) and R1 = methyl and tert-butyl, R2 = 2-(N-ethyl) pyridine for L(3-4)]. A UV-vis spectrophotometric study using 3,5-di-tert butylcatechol (3,5-DTBC) reveals that all the complexes are highly active in catalyzing the aerobic oxidation of (3,5-DTBC) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) in methanol medium with the formation of hydrogen peroxide. An EPR study confirms the generation of radicals during the catalysis. Cyclic voltammetric studies of the complexes in the presence and absence of 3,5-DTBC have been performed. Reduction of Ni(II) to Ni(I) and that of the imine bond of the ligand system have been detected at ∼-1.0 V and ∼-1.5 V, respectively. Coulometric separation of the species at -1.5 V followed by the EPR study at 77 K confirms the species as an organic radical and thus most probably reduced imine species. Spectroelectrochemical analysis at -1.5 V clearly indicates the oxidation of 3,5-DTBC and thus suggests that the radical pathway is supposed to be responsible for the catecholase-like activity exhibited by the nickel complexes. The ligand centred radical generation has further been verified by density functional theory calculation.

(N-Benzyl-N-ethyl­dithio­carbamato)di-tert-butyl­chloridotin(IV)

PubMed Central

Abdul Muthalib, Amirah Faizah; Baba, Ibrahim; Mohamed Tahir, Mohamed Ibrahim; Tiekink, Edward R. T.

2011-01-01

The SnIV atom in the title diorganotin dithio­carbamate, [Sn(C4H9)2Cl(C10H12NS2)], is penta­coordinated by an asymmetrically coordinating dithio­carbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups. The resulting C2ClS2 donor set defines a coordination geometry inter­mediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. In the crystal structure, C—H⋯π contacts link centrosymmetrically related mol­ecules into dimeric aggregates. PMID:21522295

Synthesis, structural characterization and theoretical studies of a new Schiff base 4-(((3-(tert-Butyl)-(1-phenyl)pyrazol-5-yl) imino)methyl)phenol

NASA Astrophysics Data System (ADS)

Cuenú, Fernando; Londoño-Salazar, Jennifer; Torres, John Eduard; Abonia, Rodrigo; D'Vries, Richard F.

2018-01-01

4-(((3-(tert-Butyl)-(1-phenyl)pyrazol-5-yl)imino)methyl)phenol (4-OHFPz) was synthesized and characterized by FT-IR, MS, NMR, and single-crystal X-ray diffraction. Optimization of molecular geometry, vibrational frequencies, and chemical shifts were calculated by using the methods of density functional theory (DFT) with B3LYP and B3PW91 as functionals and Hartree-Fock with 6-311G++(d,p) as basis set using the GAUSSIAN 09 program package. With the VEDA 4 software, the vibrational frequencies were assigned in terms of the potential energy distribution (PED). The equilibrium geometries calculated by all methods were compared with X-ray diffraction results, indicating that the theoretical results matches well with the experimental ones. The data obtained from the vibrational analysis and the calculated NMR are consistent with the experimental spectra.

21 CFR 177.2480 - Polyoxymethylene homopolymer.

Code of Federal Regulations, 2014 CFR

2014-04-01

... in its production. The quantity of any optional adjuvant substance employed in the production of the...), weight ratio 6/1 Do. Tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane At a maximum...

Crystal structure of (2,2′-bi­pyridine-κ2 N,N′)bis­(3,5-di-tert-butyl-o-benzo­quinonato-κ2 O,O′)ruthenium(II)

PubMed Central

Ali, Akram; Potaskalov, Vadim A.

2017-01-01

In the title mononuclear complex, [Ru(C14H20O2)2(C10H8N2)], the RuII ion has a distorted octa­hedral coordination environment defined by two N atoms of the chelating 2,2′-bi­pyridine ligand and four O atoms from two 3,5-di-tert-butyl-o-benzo­quinone ligands. In the crystal, the complex mol­ecules are linked by inter­molecular C—H⋯O hydrogen bonds and π–π stacking inter­actions between the 2,2′-bi­pyridine ligands [centroid–centroid distance = 3.538 (3) Å], resulting in a layer structure extending parallel to the ab plane. PMID:28316832

Microwave-assisted synthesis and crystal structure of oxo(diperoxo)(4,4'-di-tert-butyl-2,2'-bipyridine)-molybdenum(VI).

PubMed

Amarante, Tatiana R; Almeida Paz, Filipe A; Gago, Sandra; Gonçalves, Isabel S; Pillinger, Martyn; Rodrigues, Alírio E; Abrantes, Marta

2009-09-16

The oxodiperoxo complex MoO(O2)(2)(tbbpy) (tbbpy = 4,4'-di-tert-butyl-2,2'- bipyridine) was isolated from the reaction of MoO2Cl(2)(tbbpy) in water under microwaveassisted heating at 120 masculineC for 4 h. The structure of the oxodiperoxo complex was determined by single crystal X-ray diffraction. The Mo(VI) centre is seven-coordinated with a geometry which strongly resembles a highly distorted bipyramid. Individual MoO(O2)(2)(tbbpy) complexes are interdigitated along the [010] direction to form a column. The crystal structure is formed by the close packing of the columnar-stacked complexes. Interactions between neighbouring columns are essentially of van der Waals type mediated by the need to effectively fill the available space.

Improving the Safety of Lithium-Ion Battery via a Redox Shuttle Additive 2,5-Di- tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB).

PubMed

Leonet, Olatz; Colmenares, Luis C; Kvasha, Andriy; Oyarbide, Mikel; Mainar, Aroa R; Glossmann, Tobias; Blázquez, J Alberto; Zhang, Zhengcheng

2018-03-21

2,5-Di- tert-butyl-1,4-bis(2-methoxyethoxy)benzene (DBBB) is studied as a redox shuttle additive for overcharge protection for a 1.5 Ah graphite/C-LFP lithium-ion pouch cell for the first time. The electrochemical performance demonstrated that the protecting additive remains inert during the extended standard cycling for 4000 cycles. When a 100% overcharge is introduced in the charging protocol, the baseline cell fails rapidly during the first abusive event, whereas the cell containing DBBB additive withstands 700 overcharge cycles with 87% capacity retention and no gas evolution or cell swelling was observed. It is the first time the effectiveness of the DBBB as overcharge protection additive in a large pouch cell format is demonstrated.

Comparative transcriptome analysis of Methylibium petroleiphilum PM1 exposed to the fuel oxygenates methyl tert-butyl ether and ethanol.

PubMed

Hristova, Krassimira R; Schmidt, Radomir; Chakicherla, Anu Y; Legler, Tina C; Wu, Janice; Chain, Patrick S; Scow, Kate M; Kane, Staci R

2007-11-01

High-density whole-genome cDNA microarrays were used to investigate substrate-dependent gene expression of Methylibium petroleiphilum PM1, one of the best-characterized aerobic methyl tert-butyl ether (MTBE)-degrading bacteria. Differential gene expression profiling was conducted with PM1 grown on MTBE and ethanol as sole carbon sources. Based on microarray high scores and protein similarity analysis, an MTBE regulon located on the megaplasmid was identified for further investigation. Putative functions for enzymes encoded in this regulon are described with relevance to the predicted MTBE degradation pathway. A new unique dioxygenase enzyme system that carries out the hydroxylation of tert-butyl alcohol to 2-methyl-2-hydroxy-1-propanol in M. petroleiphilum PM1 was discovered. Hypotheses regarding the acquisition and evolution of MTBE genes as well as the involvement of IS elements in these complex processes were formulated. The pathways for toluene, phenol, and alkane oxidation via toluene monooxygenase, phenol hydroxylase, and propane monooxygenase, respectively, were upregulated in MTBE-grown cells compared to ethanol-grown cells. Four out of nine putative cyclohexanone monooxygenases were also upregulated in MTBE-grown cells. The expression data allowed prediction of several hitherto-unknown enzymes of the upper MTBE degradation pathway in M. petroleiphilum PM1 and aided our understanding of the regulation of metabolic processes that may occur in response to pollutant mixtures and perturbations in the environment.

Long-term study of migration of volatile organic compounds from cross-linked polyethylene (PEX) pipes and effects on drinking water quality.

PubMed

Lund, Vidar; Anderson-Glenna, Mary; Skjevrak, Ingun; Steffensen, Inger-Lise

2011-09-01

The objectives of this study were to investigate migration of volatile organic compounds (VOCs) from cross-linked polyethylene (PEX) pipes used for drinking water produced by different production methods, and to evaluate their potential risk for human health and/or influence on aesthetic drinking water quality. The migration tests were carried out in accordance with EN-1420-1, and VOCs were analysed by gas chromatography-mass spectrometry. The levels of VOC migrating from new PEX pipes were generally low, and decreasing with time of pipe use. No association was found between production method of PEX pipes and concentration of migration products. 2,4-di-tert-butyl phenol and methyl tert-butyl ether (MTBE) were two of the major individual components detected. In three new PEX pipes, MTBE was detected in concentrations above the recommended US EPA taste and odour value for drinking water, but decreased below this value after 5 months in service. However, the threshold odour number (TON) values for two pipes were similar to new pipes even after 1 year in use. For seven chemicals for which conclusions on potential health risk could be drawn, this was considered of no or very low concern. However, odour from some of these pipes could negatively affect drinking water for up to 1 year.

Synthesis, characterization and properties of some divalent metal(II) complexes: Their electrochemical, catalytic, thermal and antimicrobial activity studies

NASA Astrophysics Data System (ADS)

Tümer, Mehmet; Ekinci, Duygu; Tümer, Ferhan; Bulut, Akif

2007-07-01

In this study, we synthesized the amine compound 2-(2-aminoethyliminomethyl)phenol (H 3A) as the starting material, and then we prepared the polydentate Schiff base ligands from the reactions of the amine compound (H 3A) with phtaldialdehyde (H 2L), 4-methyl-2,6-di-formlyphenol (H 3L 1) and 4- t-butyl-2,6-di-formylphenol (H 3L 2) in the ethanol solution. Moreover, the complexes Cd(II), Cu(II), Co(II), Ni(II), Zn(II) and Sn(II) of the ligands H 2L, H 3L 1 and H 3L 2 have been prepared. All compounds have been characterized by the analytical and spectroscopic methods. In addition, the magnetic susceptibility and molar conductance measurements have been made. The catalytic properties of the mono- and binuclear Co(II) and Cu(II) complexes have been studied on the 3,5-di- tert-butylcatechol (3,5-DTBC) and ascorbic acid (aa) as a substrate. The oxidative C-C coupling properties of the Co(II) and Cu(II) complexes have been investigated on the sterically hindered 2,6-di- tert-butylphenol (dtbp). The antimicrobial activity properties of the ligands and their mono- and binuclear complexes have been studied against the bacteria and fungi. The results have been compared to the antibacterial and fungi drugs. The TGA curves show that the decomposition takes place in three steps for all complexes. Electrochemical properties of the complexes Cu(II) and Ni(II) have been investigated for the first time in acetonitrile by cyclic voltammetry.

On the competition between weak O-H···F and C-H···F hydrogen bonds, in cooperation with C-H···O contacts, in the difluoromethane – tert-butyl alcohol cluster

PubMed Central

Spada, Lorenzo; Tasinato, Nicola; Bosi, Giulio; Vazart, Fanny; Barone, Vincenzo; Puzzarini, Cristina

2017-01-01

The 1:1 complex of tert-butyl alcohol with difluoromethane has been characterized by means of a joint experimental-computational investigation. Its rotational spectrum has been recorded by using a pulsed-jet Fourier-Transform microwave spectrometer. The experimental work has been guided and supported by accurate quantum-chemical calculations. In particular, the computed potential energy landscape pointed out the formation of three stable isomers. However, the very low interconversion barriers explain why only one isomer, showing one O-H···F and two C-H···O weak hydrogen bonds, has been experimentally characterized. The effect of the H → tert-butyl- group substitution has been analyzed from the comparison to the difluoromethane-water adduct. PMID:28919646

40 CFR 464.11 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

.... fluoranthene 44. methylene chloride (dichloromethane) 65. phenol 66. bis(2-ethylhexyl) phthalate 67. butyl benzyl phthalate 84. pyrene 85. tetrachloroethylene 87. trichloroethylene (2) Die Casting (§ 464.15(c...) phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 72. benzo (a)anthracene...

40 CFR 464.11 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

.... fluoranthene 44. methylene chloride (dichloromethane) 65. phenol 66. bis(2-ethylhexyl) phthalate 67. butyl benzyl phthalate 84. pyrene 85. tetrachloroethylene 87. trichloroethylene (2) Die Casting (§ 464.15(c...) phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 72. benzo (a)anthracene...

Phenoxide and alkoxide complexes of Mg, Al and Zn, and their use for the ring-opening polymerization of ℇ-caprolactone with initiators of different natures.

PubMed

Minyaev, Mikhail E; Nifant'ev, Ilya E; Shlyakhtin, Andrey V; Ivchenko, Pavel V; Lyssenko, Konstantin A

2018-05-01

A new packing polymorph of bis(2,6-di-tert-butyl-4-methylphenolato-κO)bis(tetrahydrofuran-κO)magnesium, [Mg(C 15 H 23 O) 2 (C 4 H 8 O) 2 ] or Mg(BHT) 2 (THF) 2 , (BHT is the 2,6-di-tert-butyl-4-methylphenoxide anion and THF is tetrahydrofuran), (1), has the same space group (P2 1 ) as the previously reported modification [Nifant'ev et al. (2017d). Dalton Trans. 46, 12132-12146], but contains three crystallographically independent molecules instead of one. The structure of (1) exhibits rotational disorder of the tert-butyl groups and positional disorder of a THF ligand. The complex of bis(2,6-di-tert-butyl-4-methylphenolato-κO)bis(μ 2 -ethyl glycolato-κ 2 O,O':κO)dimethyldialuminium, [Al 2 (CH 3 ) 2 (C 4 H 7 O 3 ) 2 (C 15 H 23 O) 2 ] or [(BHT)AlMe(OCH 2 COOEt)] 2 , (2), is a dimer located on an inversion centre and has an Al 2 O 2 rhomboid core. The 2-ethoxy-2-oxoethanolate ligand (OCH 2 COOEt) displays a μ 2 -κ 2 O,O':κO semi-bridging coordination mode, forming a five-membered heteronuclear Al-O-C-C-O ring. The same ligand exhibits positional disorder of the terminal methyl group. The redetermined structure of the heptanuclear complex octakis(μ 3 -benzyloxo-κO:κO:κO)hexaethylheptazinc, [Zn 7 (C 2 H 5 ) 6 (C 7 H 7 O) 8 ] or [Zn 7 (OCH 2 Ph) 8 Et 6 ], (3), possesses a bicubic Zn 7 O 8 core located at an inversion centre and demonstrates positional disorder of one crystallographically independent phenyl group. Cambridge Structural Database surveys are given for complexes structurally analogous to (2) and (3). Complexes (2) and (3), as well as derivatives of (1), are of interest as catalysts for the ring-opening polymerization of ℇ-caprolactone, and polymerization results are reported.

Acetylcholinesterase and Acetylcholine Receptor

DTIC Science & Technology

1989-01-30

trimethyl analogue, neopentyl alcohol, (CH 3 ) 3 CCH20H, Ki(comi - 29 mM, Ki(nonc)’ = 74 mM, and to the ether isomer of the latter, =-butyl methyl ether, (CH...Trietrylene glycol di-tert-butylether is being prepared from the glycol via the di-p-toluenesulfonate, mp 80-81"C from methanol, lit. 80-810C (60). 2-N,N

Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment.

PubMed

Rampazzi, Vincent; Roger, Julien; Amardeil, Régine; Penouilh, Marie-José; Richard, Philippe; Fleurat-Lessard, Paul; Hierso, Jean-Cyrille

2016-11-07

A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis(5-methyl-2-furyl)phosphino]-3,3'-di-tert-butylferrocene (5-r), and rac-1,1'-bis(diphenylphosphino)-3,3'-bis[(tri-iso-propylsilyl)oxy]ferrocene (6-r) were used to form dinuclear gold complexes. Coordination of tert-butylated ferrocenyl phosphines generated aurophilic interactions in the corresponding dinuclear gold complexes, contrary to gold(I) complexes reported with 1,1'-bis(diphenylphosphino)ferrocene. The structurally related tetraphosphine 1,1',2,2'-tetrakis(diphenylphosphino)-4,4'-di-tert-butylferrocene (11) also gave access to mononuclear, dinuclear, and the original trinuclear gold chloride aurophilic complexes in which 14e - to 16e - gold centers coexist. In such complexes, nonbonded ("through-space") 31 P- 31 P' nuclear spin couplings were evidenced by high-resolution NMR. In these interactions nuclear spin information is transferred between the lone-pair electron of an uncoordinated phosphorus P and a phosphorus P' that is involved in a σ covalent bond Au-P'. The dinuclear aurophilic complex displayed a concerted shuttling of its [ClAu···AuCl] fragment between the four phosphorus donors of the tetraphosphine ligand. Thus, an aurophilic Au···Au bond, which is assumed to be a weak energy interaction, can be conserved within a dynamic shuttling process at high temperature involving an intramolecular coordination-decoordination process of digold(I) at phosphorus atoms.

Single sensor for multiple analytes in different optical channel: Applying for multi-ion response modulation

NASA Astrophysics Data System (ADS)

Liang, Chunshuang; Jiang, Shimei

2017-08-01

A Schiff-base, (2,4-di-tert-butyl-6-((2-hydroxyphenyl-imino)-methyl)phenol) (L), has been improved to function as a simultaneous multi-ion probe in different optical channel. The probe changes from colorless to orangish upon being deprotonated by F-, while the presence of Al3+ significantly enhances the fluorescence of the probe due to the inhibition of Cdbnd N isomerization, cation-induced inhibition of excited-state intramolecular proton transfer (ESIPT), and chelation enhanced fluorescence (CHEF). Dual-channel "off-on" switching behavior resulted from the sequential input of F- and Al3+, reflecting the balance of independent reactions of Al3+ and F- with L and with one another. This sensing phenomenon realizes transformation between multiple states and beautifully mimics a "Write-Read-Erase-Read" logic circuit with two feedback loops.

Production of o-diphenols by immobilized mushroom tyrosinase.

PubMed

Marín-Zamora, María Elisa; Rojas-Melgarejo, Francisco; García-Cánovas, Francisco; García-Ruiz, Pedro Antonio

2009-01-15

The o-diphenols 4-tert-butyl-catechol, 4-methyl-catechol, 4-methoxy-catechol, 3,4-dihydroxyphenylpropionic acid and 3,4-dihydroxyphenylacetic acid were produced from the corresponding monophenols (4-tert-butyl-phenol, 4-methyl-phenol, 4-methoxy-phenol, p-hydroxyphenylpropionic acid and p-hydroxyphenylacetic acid) using immobilized mushroom tyrosinase from Agaricus bisporus. In all cases the yield was R(diphenol)> or =88-96%, which, according to the literature, is the highest yield so far, obtained using tyrosinase. The reaction was carried out in 0.5M borate buffer pH 9.0 which was used to minimize the diphenolase activity of tyrosinase by complexing the o-diphenols generated. Hydroxylamine and ascorbic acid were also present in the reaction medium, the former being used to reduce mettyrosinase to deoxytyrosinase, closing the catalytic cycle, and the latter to reduce the o-quinone produced to o-diphenol. Inactivation of the tyrosinase by ascorbic acid was also minimized due to the formation of an ascorbic acid-borate complex. Concentrations of the o-diphenolic compounds obtained at several reaction times were determined by gas chromatography-mass spectrometry (GC-MS) and UV-vis spectroscopy. The experimental results are discussed.

21 CFR 177.2470 - Polyoxymethylene copolymer.

Code of Federal Regulations, 2014 CFR

2014-04-01

... paragraph (a) of this section may contain optional adjuvant substances required in its production. The quantity of any optional adjuvant substance employed in the production of the copolymer does not exceed the... (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane. (2) Lubricant: N,N′Distearoylethyl-enediamine...

FT-IR, FT-Raman spectra, density functional computations of the vibrational spectra and molecular conformational analysis of 2,5-di-tert-butyl-hydroquinone

NASA Astrophysics Data System (ADS)

Subramanian, N.; Sundaraganesan, N.; Dereli, Ö.; Türkkan, E.

2011-12-01

The purpose of finding conformer among six different possible conformers of 2,5-di-tert-butyl-hydroquinone (DTBHQ), its equilibrium geometry and harmonic wavenumbers were calculated by the B3LYP/6-31G(d,p) method. The infrared and Raman spectra of DTBHQ were recorded in the region 400-4000 cm -1 and 50-3500 cm -1, respectively. In addition, the IR spectra in CCl 4 at various concentrations of DTBHQ are also recorded. The computed vibrational wavenumbers were compared with the IR and Raman experimental data. Computational calculations at B3LYP level with two different basis sets 6-31G(d,p) and 6-311++G(d,p) are also employed in the study of the possible conformer of DTBHQ. The complete assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA 4 program. The general agreement between the observed and calculated frequencies was established.

Flavonoids, flavonoid metabolites, and phenolic acids inhibit oxidative stress in the neuronal cell line HT-22 monitored by ECIS and MTT assay: a comparative study.

PubMed

Kling, Beata; Bücherl, Daniel; Palatzky, Peter; Matysik, Frank-Michael; Decker, Michael; Wegener, Joachim; Heilmann, Jörg

2014-03-28

A real-time and label-free in vitro assay based on electric cell-substrate impedance sensing (ECIS) was established, validated, and compared to an end-point MTT assay within an experimental trial addressing the cytoprotective effects of 19 different flavonoids, flavonoid metabolites, and phenolic acids and their methyl esters on the HT-22 neuronal cell line, after induction of oxidative stress with tert-butyl hydroperoxide. Among the flavonoids under study, only those with a catechol unit and an additional 4-keto group provided cytoprotection. The presence of a 2,3-double bond was not a structural prerequisite for a neuroprotective effect. In the case of the phenolics, catechol substitution was the only structural requirement for activity. The flavonoids and other phenolics with a ferulic acid substitution or a single hydroxy group showed no activity. Electrochemical characterization of all compounds via square-wave voltammetry provided a rather specific correlation between cytoprotective activity and redox potential for the active flavonoids, but not for the active phenolics with a low molecular weight. Moreover this study was used to compare label-free ECIS recordings with results of the established MTT assay. Whereas the former provides time-resolved and thus entirely unbiased information on changes of cell morphology that are unequivocally associated with cell death, the latter requires predefined exposure times and a strict causality between metabolic activity and cell death. However, MTT assays are based on standard lab equipment and provide a more economic way to higher throughput.

Synthesis and dynamic NMR study of ketenimines derived from tert-butyl isocyanide, alkyl 2-arylamino-2-oxo-acetates, and dialkyl acetylenedicarboxylates.

PubMed

Yavari, Issa; Nasiri, Farough; Djahaniani, Horieh

2004-01-01

The adduct produced in the reaction between tert-butyl isocyanide and dialkyl acetylenedicarboxylates was trapped by alkyl 2-arylamino-2-oxo-acetates. When the aryl group is 2-methyl-6-nitrophenyl or 2,6-di-isopropylphenyl, the product exists as two stable rotamers at room temperature as a result of restricted rotation around the Ar-N single bond. When the aryl group is 1-naphthyl or 8-quinolinyl, dynamic NMR effects are observed in the 1H NMR spectra. The calculated free-energy of activation for interconversion of the rotational isomers in 1-naphthyl and 8-quinolinyl derivatives amounts to about 99+/-2 and 68.5+/-2 kJ mol(-1), respectively.

Some features of the oxidative conversion of Mo(CO)/sub 6/ in a medium of hydroperoxide or tert-butyl hydroperoxide and an aromatic hydrocarbon

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

Fomin, V.M.; Lunin, A.V.; Aleksandrov, Yu.A.

1988-03-10

Occurrence of the reaction under study was followed from the decrease in hydroperoxide or of Mo(CO)/sub 6/. The Mo(CO)/sub 6/ content of the reaction was found by determining either the concentration of this compound directly or by determining the concentration of the gaseous products from its transformations (CO + CO/sub 2/). Hydroperoxides (I) and (II) were determined iodometrically. Metal-containing products of the oxidation of Mo(CO)/sub 6/, molybdenum oxides and peroxides, were analyzed by IR and ESR spectroscopy, elemental analysis, and iodometry. Analysis of transformation products of the hydroperoxides (phenol, acetone, dimethylphenylcarbinol, acetophenone, tert-butyl alcohol, water, and oxygen) was performed usingmore » gas chromatography. Results are presented.« less

40 CFR 464.31 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (dichloromethane) 55. naphthalene 64. pentachlorophenol 65. phenol 66. bis(2-ethylhexyl)phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72. benzo (a)anthracene (1,2... (dichloromethane) 66. bis (2-ethylhexyl) phthalate 77. acenaphthylene 84. pyrene (4) Melting Furnace Scrubber...

40 CFR 464.31 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... (dichloromethane) 55. naphthalene 64. pentachlorophenol 65. phenol 66. bis(2-ethylhexyl)phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72. benzo (a)anthracene (1,2... (dichloromethane) 66. bis (2-ethylhexyl) phthalate 77. acenaphthylene 84. pyrene (4) Melting Furnace Scrubber...

The Ketene-Surrogate Coupling: Catalytic Conversion of Aryl Iodides to Aryl Ketenes via Ynol Ethers**

PubMed Central

Zhang, Wenhan; Ready, Joseph M.

2014-01-01

tert-Butoxyacetylene is shown to undergo Sonogashira coupling with aryl iodides to yield aryl-substituted tert-butyl ynol ethers. These intermediates participate in a [1,5]-hydride shift, which results in the extrusion of isobutylene and the generation of aryl ketenes. The ketenes are trapped in situ with multiple nucleophiles or undergoelectrocyclic ring closure to yield hydroxynaphthalenes and quinolines. PMID:24975840

[18F]Fluorophenylazocarboxylates: Design and Synthesis of Potential Radioligands for Dopamine D3 and μ-Opioid Receptor

PubMed Central

2017-01-01

18F-Labeled building blocks from the type of [18F]fluorophenylazocarboxylic-tert-butyl esters offer a rapid, mild, and reliable method for the 18F-fluoroarylation of biomolecules. Two series of azocarboxamides were synthesized as potential radioligands for dopamine D3 and the μ-opioid receptor, revealing compounds 3d and 3e with single-digit and sub-nanomolar affinity for the D3 receptor and compound 4c with only micromolar affinity for the μ-opioid receptor, but enhanced selectivity for the μ-subtype in comparison to the lead compound AH-7921. A “minimalist procedure” without the use of a cryptand and base for the preparation of 4-[18F]fluorophenylazocarboxylic-tert-butyl ester [18F]2a was established, together with the radiosynthesis of methyl-, methoxy-, and phenyl-substituted derivatives ([18F]2b–f). With the substituted [18F]fluorophenylazocarbylates in hand, two prototype azocarboxylates radioligands were synthesized by 18F-fluoroarylation, namely the methoxy azocarboxamide [18F]3d as the D3 receptor radioligand and [18F]4a as a prototype structure of the μ-opioid receptor radioligand. By introducing the new series of [18F]fluorophenylazocarboxylic-tert-butyl esters, the method of 18F-fluoroarylation was significantly expanded, thereby demonstrating the versatility of 18F-labeled phenylazocarboxylates for the design of potential radiotracers for positron emission tomography . PMID:29479577

40 CFR 464.21 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

.... pentachlorophenol 66. bis(2-ethylhexyl)phthalate 71. dimethyl phthalate (2) Dust Collection Scrubbers (§ 464.25(c...-dimethylphenol 55. naphthalene 58. 4-nitrophenol 64. pentachlorophenol 65. phenol 66. bis(2-ethylhexyl)phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72...

40 CFR 464.21 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

.... pentachlorophenol 66. bis(2-ethylhexyl)phthalate 71. dimethyl phthalate (2) Dust Collection Scrubbers (§ 464.25(c...-dimethylphenol 55. naphthalene 58. 4-nitrophenol 64. pentachlorophenol 65. phenol 66. bis(2-ethylhexyl)phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72...

A Study of the Curing and Flammability Properties of Bisphenol A Epoxy Diacrylate Resin Utilizing a Novel Flame Retardant Monomer, bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl Phosphate

PubMed Central

Rwei, Syang-Peng; Chen, Yu-Ming; Chiang, Whe-Yi; Ting, Yi-Tien

2017-01-01

A UV-curable, flame-retardant monomer, DAPP (bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl-phosphate), was synthesized based on BPDCP (4-tert-butylphenyl-dichloro phosphate) and HEA (2-hydroxy ethyl acrylate). DAPP was blended with regular bisphenol A epoxy acrylate (BAEA) in various ratios to yield various phosphorus contents. The TGA-IR (thermogravimetric analyzer interface with an infrared spectrometer) results demonstrate that compounding 30 mol % DAPP with BAEA significantly reduced the amount of released CO gas. In contrast, the peak intensity of CO2 is independent of phosphorus content. The limiting oxygen index (LOI), reaching the saturated value of 26, and the heat release rate (HRR) measured using a cone-calorimeter, 156.43 KW/m2, confirm the saturation point when 30 mol % DAPP was compounded into BAEA. A study of the kinetics of pyrolysis reveals that Ea decreases as the phosphorus content increases. Both the TGA-IR and pyrolysis results reveal that the phosphorus compound DAPP is easily decomposed during the initial stage of burning to form an insulating layer, which inhibits further burning of the resin and the consequent release of other flammable gases. PMID:28772562

Screening chemical composition and in vitro antioxidant and antimicrobial activities of the essential oils from Origanum syriacum L. growing in Turkey.

PubMed

Alma, Mehmet Hakki; Mavi, Ahmet; Yildirim, Ali; Digrak, Metin; Hirata, Toshifumi

2003-12-01

In the present study, essential oil from the leaves of Syrian oreganum [Origanum syriacum L. (Lauraceae)] grown in Turkish state forests of the Dortyol district, Turkey, was obtained by steam distillation. The chemical composition of oil was analysed by GC and GC-MS, and was found to contain 49.02% monoterpenes, 36.60% oxygenated monoterpenes and 12.59% sesquiterpenes. The major components are as follows: gamma-terpinene, carvacrol, p-cymene and beta-caryophyllene. Subsequently, the reducing power, antioxidant and 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging activities of the essential oil were studied. The reducing power was compared with ascorbic acid, and the other activities were compared with 2,6-di-tert-butyl-4-methyl phenol (BHT, butylated hydroxytoluene). The results showed that the activities were concentration dependent. The antioxidant activities of the oil were slightly lower than those of ascorbic acid or BHT, so the oil can be considered an effective natural antioxidant. Antimicrobial activities of the essential oil from the leaves of Origanum syriacum was also determined on 16 microorganisms tested using the agar-disc diffusion method, and showed antimicrobial activity against 13 of these.

Geosynthesis of organic compounds: I. Alkylphenols

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

Ioppolo-Armanios, M.; Alexander, R.; Kagi, R.I.

1995-07-01

Methylation, isopropylation, and sec-butylation are proposed as geosynthetic processes to account for the alkylphenol compositions of crude oils with phenol distributions dominated by ortho and para substituted compounds. Phenol distributions in eleven crude oils and four kerogen pyrolysates were analysed using GC-MS (gas chromatography-mass spectrometry). Ten of the crude oils show high relative abundances of ortho and para substituted phenol isomers and some were also enriched in C{sub 3}-C{sub 5} alkylphenols compared to the kerogen pyrolysates. Because the distributions of products obtained from the laboratory alkylation of cresols closely resemble those of phenols in these crude oils, we propose thatmore » similar alkylation processes occur in source rocks. Alkylation ratios reflecting the degree of methylation, isopropylation, and sec-butylation, which were based on the relative abundance of the dominant alkylation products compared to their likely precursor ortho-cresol, indicate that high levels of methylation occurred in crude oils over a wide range of maturities, whereas high levels of isopropylation and sec-butylation were observed only in mature samples. Dissolution of the phenols in crude oils by water contact was discounted as an explanation for the observed phenol distributions based on the relative distribution coefficients of phenols between a hydrocarbon phase and water.« less

C60 Recognition from Extended Tetrathiafulvalene Bis-acetylide Platinum(II) Complexes.

PubMed

Bastien, Guillaume; Dron, Paul I; Vincent, Manon; Canevet, David; Allain, Magali; Goeb, Sébastien; Sallé, Marc

2016-11-18

The favorable spatial organization imposed by the square planar 4,4'-di(tert-butyl)-2,2'-bipyridine (dbbpy) platinum(II) complex associated with the electronic and shape complementarity of π-extended tetrathiafulvalene derivatives (exTTF) toward fullerenes is usefully exploited to construct molecular tweezers, which display good affinities for C 60 .

21 CFR 175.105 - Adhesives.

Code of Federal Regulations, 2013 CFR

2013-04-01

...) content averages 9 or 30 moles endo-cis-5-Norbornene-2,3-dicarboxylic anhydride α-cis-9-Octadecenyl-omega...) Potassium tripolyphosphate α, α′, α″-1,2,3-Propanetriyltris [omega-(2,3-epoxypropoxy) poly (oxypropylene... (3,5-di-tert-butyl-4-hydroxy-hydro-cinnamate)] methane a[p-(1,1,3,3-Tetramethylbutyl) phenyl]-omega...

21 CFR 175.105 - Adhesives.

Code of Federal Regulations, 2012 CFR

2012-04-01

...) content averages 9 or 30 moles endo-cis-5-Norbornene-2,3-dicarboxylic anhydride α-cis-9-Octadecenyl-omega...) Potassium tripolyphosphate α, α′, α″-1,2,3-Propanetriyltris [omega-(2,3-epoxypropoxy) poly (oxypropylene... (3,5-di-tert-butyl-4-hydroxy-hydro-cinnamate)] methane a[p-(1,1,3,3-Tetramethylbutyl) phenyl]-omega...

21 CFR 175.105 - Adhesives.

Code of Federal Regulations, 2014 CFR

2014-04-01

...) content averages 9 or 30 moles endo-cis-5-Norbornene-2,3-dicarboxylic anhydride α-cis-9-Octadecenyl-omega...) Potassium tripolyphosphate α, α′, α″-1,2,3-Propanetriyltris [omega-(2,3-epoxypropoxy) poly (oxypropylene... (3,5-di-tert-butyl-4-hydroxy-hydro-cinnamate)] methane a[p-(1,1,3,3-Tetramethylbutyl) phenyl]-omega...

Antioxidant capacity of BO-653, 2,3-dihydro-5-hydroxy-4,6-di-tert-butyl-2,2-dipentylbenzofuran, and uric acid as evaluated by ORAC method and inhibition of lipid peroxidation.

PubMed

Niki, Etsuo; Fukuhara, Akiko; Omata, Yo; Saito, Yoshiro; Yoshida, Yasukazu

2008-04-01

The role of radical-scavenging antioxidant against oxidative stress has received much attention. The antioxidant capacity has been assessed by various methods. Above all, oxygen radical absorbance capacity (ORAC) has been frequently employed [Prior et.al., J. Agric. Food Chem.2005, 53, 4290]. In the present study, the antioxidant capacity of 2,3-dihydro-5-hydroxy-4,6-di-tert-butyl-2,2-dipentylbenzofuran (BO-653) and uric acid was assessed by ORAC method using pyranine as a reference probe and compared with that against lipid peroxidation of human plasma. It was found that BO-653 was assessed to be much less potent than uric acid by ORAC method, whereas BO-653 exerted much higher antioxidant activity than uric acid against plasma lipid peroxidation. The reason for such discrepancy is discussed. The results suggest that ORAC method is suitable for the assessment of free radical scavenging capacity, but not for the assessment of antioxidant capacity against lipid peroxidation in plasma.

Enantiodifferentiation of whisky and cognac lactones using gas chromatography with different cyclodextrin chiral stationary phases.

PubMed

Schmarr, Hans-Georg; Mathes, Maximilian; Wall, Kristina; Metzner, Frank; Fraefel, Marius

2017-09-22

The chiral lactone 5-butyl-4-methyloxolan-2-one or 5-butyl-4-methyldihydro-2(3H)-furanone, often named whisky lactone, is found in oak wood, then contributing to the appreciated flavor of beverages stored in such wooden barrels. Its next higher homologue is named cognac lactone (5-pentyl-4-methyloxolan-2-one or 5-pentyl-4-methyldihydro-2(3H)-furanone), however is much less known, probably due to its minor concentration level. In order to study the direct enantioseparation of both lactones by gas chromatography on chiral stationary phases, individual enantiomers, particularly for cognac lactone were made available. This was achieved by baker's yeast reduction of synthesized ethyl 3-methyl-4-oxononanoate or, after hydrolysis, of the corresponding 4-ketoacid, that gave access to individual enantiomers of cognac lactone. Good enantioseparation was achieved for both whisky and cognac lactone with high values for the chiral resolution with 6-O-tert. butyl dimethylsilyl-2,3-dialkylated or 6-O-tert. butyl dimethylsilyl-2,3-diacylated cyclodextrin derivatives as chiral selectors. The influence of the nature and position of derivatization of the cyclodextrin moiety revealed a strong impact on the chiral recognition mechanism, as the investigated alkylated derivatives heptakis-(2,6-di-O-iso-pentyl-3-O-allyl)-β-cyclodextrin and octakis-(2,3-di-O-pentyl-6-O-methyl)-γ-cyclodextrin did not provide any or only minor chiral selectivity for the two lactones. Copyright © 2017 Elsevier B.V. All rights reserved.

40 CFR 469.12 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... methylene chloride naphthalene 2 Nitrophenol phenol bis (2-ethylhexyl) phthalate tetrachloroethylene toluene trichloroethylene 2 Chlorophenol 2,4 Dichlorophenol 4 Nitrophenol pentachlorophenol di-n-butyl phthalate anthracene...

40 CFR 469.12 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... methylene chloride naphthalene 2 Nitrophenol phenol bis (2-ethylhexyl) phthalate tetrachloroethylene toluene trichloroethylene 2 Chlorophenol 2,4 Dichlorophenol 4 Nitrophenol pentachlorophenol di-n-butyl phthalate anthracene...

Functional electrolyte for lithium-ion batteries

DOEpatents

Zhang, Lu; Zhang, Zhengcheng; Amine, Khalil

2015-04-14

Functional electrolyte solvents include compounds having at least one aromatic ring with 2, 3, 4 or 5 substituents, at least one of which is a substituted or unsubstituted methoxy group, at least one of which is a tert-butyl group and at least one of which is a substituted or unsubstituted polyether or poly(ethylene oxide) (PEO) group bonded through oxygen to the aromatic ring, are provided.

Bis-Aryloxalates as Convenient Unimolecular Sources of Aryloxyl Radicals

DTIC Science & Technology

1990-03-06

Research Tower Department of Chemistry, University of Massachusetts, Amherst, MA 01003 ii Synthesis of Diphenyl Oxalate : This general reaction is a useful...preparative method for any unhindered diaryl oxalate . Phenol was used as received. Oxalyl chloride was distilled under vacuum. Pyridine was distilled...Found C 79.12 H 9.93. iii Bis(4-Methoxy-2.6-di-t-butylphenyl) oxalate : Oxalyl chloride was distilled under vacuum. 4-Methoxy-2,6-di-t-butyl phenol was

4,5-Dibromo-2,7-di-tert-butyl-9,9-dimethyl-9H-thioxanthene

PubMed Central

Rubio, Omayra H.; Fuentes de Arriba, Angel L.; Sanz, Francisca; Muniz, Francisco M.; Morán, Joaquín R.

2012-01-01

In the title compound, C23H28Br2S, the thioxanthene unit is twisted, showing a dihedral angle of 29.3 (5)° between the benzene rings. When projected along [001], the packing shows two types of channels. The crystal studied was a racemic twin. PMID:22719586

Regioisomer-Free C 4h β-Tetrakis(tert-butyl)metallo-phthalocyanines: Regioselective Synthesis and Spectral Investigations.

PubMed

Iida, Norihito; Tanaka, Kenta; Tokunaga, Etsuko; Takahashi, Hiromi; Shibata, Norio

2015-04-01

Metal β-tetrakis(tert-butyl)phthalocyanines are the most commonly used phthalocyanines due to their high solubility, stability, and accessibility. They are commonly used as a mixture of four regioisomers, which arise due to the tert-butyl substituent on the β-position, and to the best of our knowledge, their regioselective synthesis has yet to be reported. Herein, the C 4h -selective synthesis of β-tetrakis(tert-butyl)metallophthalocyanines is disclosed. Using tetramerization of α-trialkylsilyl phthalonitriles with metal salts following acid-mediated desilylation, the desired metallophthalocyanines were obtained in good yields. Upon investigation of regioisomer-free zinc β-tetrakis(tert-butyl)phthalocyanine using spectroscopy, the C 4h single isomer described here was found to be distinct in the solid state to zinc β-tetrakis(tert-butyl)phthalocyanine obtained by a conventional method.

Crystal structure of bis­{μ-(E)-2-[(2-oxido­phenyl­imino)­meth­yl]quinolin-8-olato-κ4 O,N,N′,O′}bis­[di­butyl­tin(IV)

PubMed Central

Carlos, Camacho-Camacho; Naytzé, Ortiz-Pastrana; Ariadna, Garza-Ortiz; Irma, Rojas-Oviedo

2017-01-01

Condensation of 8-hy­droxy­quinoline-2-carbaldehyde with 2-amino­phenol gave the (E)-2-[(2-hy­droxy­phenyl­imino)­meth­yl]quinolin-8-ol derivative that reacted with di-n-butyl­tin oxide with release of H2O to yield the chelate title complex, [Sn2(C4H9)4(C16H10N2O2)2]. The compound crystallizes in the triclinic space group P-1, with two independent centrosymmetric dimers in the unit cell. Each features a typical pincer-type structure where the dianionic ligand is tetra­dentate, coordinating to the central tin atom through both phenolate oxygen atoms, as well as through the quinoline and imine N atoms. Each metal atom adopts a distorted penta­gonal–bipyramidal SnC2N2O3 coordination arising from the N,N′,O,O′-tetra­dentate deprotonated Schiff base, one bridging phenolate O atom of the neighbouring ligand and two butyl groups in the axial sites. PMID:28083122

N-heterocycle carbene (NHC)-ligated cyclopalladated N,N-dimethylbenzylamine: a highly active, practical and versatile catalyst for the Heck-Mizoroki reaction.

PubMed

Peh, Guang-Rong; Kantchev, Eric Assen B; Zhang, Chi; Ying, Jackie Y

2009-05-21

The wide dissemination of catalytic protocols in academic and industrial laboratories is facilitated by the development of catalysts that are not only highly active but also user-friendly, stable to moisture, air and long term storage and easy to prepare on a large scale. Herein we describe a protocol for the Heck-Mizoroki reaction mediated by cyclopalladated N,N-dimethylbenzylamine (dmba) ligated with a N-heterocyclic carbene, 1,3-bis(mesityl)imidazol-2-ylidene (IMes), that fulfils these criteria. The precatalyst can be synthesized on approximately 100 g scale by a tri-component, sequential, one-pot reaction of N,N-dimethylbenzylamine, PdCl2 and IMes.HCl in refluxing acetonitrile in air in the presence of K2CO3. This single component catalyst is stable to air, moisture and long term storage and can be conveniently dispensed as a stock solution in NMP. It mediates the Heck-Mizoroki reaction of a range of aryl- and heteroaryl bromides in reagent grade NMP at the 0.1-2 mol% range without the need for rigorous anhydrous techniques or a glovebox, and is active even in air. The catalyst is capable of achieving very high levels of catalytic activity (TON of up to 5.22 x 10(5)) for the coupling of a deactivated arylbromide, p-bromoanisole, with tBu acrylate as a benchmark substrate pair. A wide range of aryl bromides, iodides and, for the first time with a NHC-Pd catalyst, a triflate was coupled with diverse acrylate derivatives (nitrile, tert-butyl ester and amides) and styrene derivatives. The use of excess (>2 equiv.) of the aryl bromide and tert-butyl acrylate leads to mixture of tert-butyl beta,beta-diarylacrylate and tert-butyl cinnamate derivatives depending on the substitution pattern of the aryl bromide. Electron rich m- and p-substituted arylbromides give the diarylated products exclusively, whereas electron-poor aryl bromides give predominantly mono-arylated products. For o-substituted aryl bromides, no doubly arylated products could be obtained under any conditions. Overall, the active catalyst (IMes-Pd) shows higher activity with electron-rich aryl halides, a marked difference compared with the more commonly used phosphane-Pd or non-ligated Pd catalysts.

27 CFR 21.101 - tert-Butyl alcohol.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false tert-Butyl alcohol. 21.101....101 tert-Butyl alcohol. (a) Acidity (as acetic acid). 0.003 percent by weight maximum. (b) Color. Colorless. (c) Distillation range. When 100 ml of tertiary butyl alcohol are distilled, none should distill...

27 CFR 21.101 - tert-Butyl alcohol.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false tert-Butyl alcohol. 21.101....101 tert-Butyl alcohol. (a) Acidity (as acetic acid). 0.003 percent by weight maximum. (b) Color. Colorless. (c) Distillation range. When 100 ml of tertiary butyl alcohol are distilled, none should distill...

Simultaneous analysis of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils by normal-phase high performance liquid chromatography.

PubMed

Li, Jun; Bi, Yanlan; Sun, Shangde; Peng, Dan

2017-11-01

A normal-phase high performance liquid chromatography method for the simultaneous determination of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils was investigated. A silica column was used to separate the analytes with the gradient elution. An ultraviolet-visible detector was set at dual wavelengths mode (280 and 310nm). The column temperature was 30°C. The analytes were directly extracted with methanol. Results showed that the normal-phase high performance liquid chromatography method performed well with wide liner ranges (0.10∼500.00μg/mL, R 2 >0.9998), low limits of detection and quantitation (below 0.40 and 1.21μg/mL, respectively), and good recoveries (81.38∼102.34% in soybean oils and 83.03∼100.79% in lard, respectively). The reduction of tert-butylquinone caused by the reverse-phase high performance liquid chromatography during the injection was avoided with the current normal-phase method. The two isomers of butylated hydroxyanisole can also be separated with good resolution. Copyright © 2017 Elsevier Ltd. All rights reserved.

New fluorescent perylene bisimide indicators--a platform for broadband pH optodes.

PubMed

Aigner, Daniel; Borisov, Sergey M; Klimant, Ingo

2011-06-01

Asymmetric perylene bisimide (PBI) dyes are prepared and are shown to be suitable for the preparation of fluorescence chemosensors for pH. They carry one amino-functional substituent which introduces pH sensitivity via photoinduced electron transfer (PET) while the other one increases solubility. The luminescence quantum yields for the new indicators exceed 75% in the protonated form. The new indicators are non-covalently entrapped in polyurethane hydrogel D4 and poly(hydroxyalkylmethacrylates). Several PET functions including aliphatic and aromatic amino groups were successfully used to tune the dynamic range of the sensor. Because of their virtually identical spectral properties, various PBIs with selected PET functions can easily be integrated into a single sensor with enlarged dynamic range (over 4 pH units). PBIs with two different substitution patterns in the bay position are investigated and possess variable spectral properties. Compared with their tetrachloro analogues, tetra-tert-butyl-substituted PBIs yield more long-wave excitable sensors which feature excellent photostability. Cross-sensitivity to ionic strength was found to be negligible. The practical applicability of the sensors may be compromised by the long response times (especially in case of tetra-tert-butyl-substituted PBIs).

Synthesis of Polystyrene and Molecular Weight Determination by [superscript 1]H NMR End-Group Analysis

ERIC Educational Resources Information Center

Wackerly, Jay Wm.; Dunne, James F.

2017-01-01

A procedure for the solution polymerization of styrene using di-"tert"-butyl peroxide (DTBP) as the initiator is described. The use of DTBP allows for end-group analysis by [superscript 1]H NMR spectroscopy and calculation of the number-average molecular weight of the polymer. This experiment was designed as a laboratory introduction to…

[Chemical constituents of Jasminum giraldii and their antioxidant activity].

PubMed

Zhang, Xiu-Peng; Qin, Hui; Yang, Fang; Chai, Jiang; Wang, Xin; Song, Xiao-Mei; Mei, Qi-Bing; Feng, Feng; Yue, Zheng-Gang

2014-06-01

Ten compounds were isolated from the barks of Jasminum giraldii by means of various of chromatographic techniques such as silica gel, Sephadex LH-20 and Rp-HPLC. Their structures were identified by spectroscopic data analysis as (+)-medioresinol (1), (+) -syringaresinol (2), syringaresinol-4'-O-beta-D-glucopyranoside (3), oleanic acid (4), 3-methoxy-4-hydroxy-trans-cinnamaldehyde (5), trans-sinapaldehyde (6), syringaldehyde (7), 1-(4-methoxy -phenyl) -ethanol (8), trans-cinnamic acid (9), and 4-(1-methoxyethyl) -phenol (10). Among them, compounds 1-3, 5-8 and 10 were isolated from the J. genus for the first time and compounds 4 and 9 were obtained from J. giraldii for the first time. In the DPPH free radical scavenging assay, compound 1 exhibited significant activity (IC50 55.1 micromol x L(-1)), compared with vitamin C(IC50 59.9 micromol x L(-1)); and compound 2 showed moderate activity (IC50 79.0 micromol x L(-1)), compared with 2, 6-di-tert-butyl4-methylphenol (IC50 236 micromol x L(-1)).

Contamination of packaged food by substances migrating from a direct-contact plastic layer: Assessment using a generic quantitative household scale methodology.

PubMed

Vitrac, Olivier; Challe, Blandine; Leblanc, Jean-Charles; Feigenbaum, Alexandre

2007-01-01

The contamination risk in 12 packaged foods by substances released from the plastic contact layer has been evaluated using a novel modeling technique, which predicts the migration that accounts for (i) possible variations in the time of contact between foodstuffs and packaging and (ii) uncertainty in physico-chemical parameters used to predict migration. Contamination data, which are subject to variability and uncertainty, are derived through a stochastic resolution of transport equations, which control the migration into food. Distributions of contact times between packaging materials and foodstuffs were reconstructed from the volumes and frequencies of purchases of a given panel of 6422 households, making assumptions about household storage behaviour. The risk of contamination of the packaged foods was estimated for styrene (a monomer found in polystyrene yogurt pots) and 2,6-di-tert-butyl-4-hydroxytoluene (a representative of the widely used phenolic antioxidants). The results are analysed and discussed regarding sensitivity of the model to the set parameters and chosen assumptions.

Distribution of methyl tert-butyl ether (MTBE) and selected water-quality constituents in the surficial aquifer at the Dover National Test Site, Dover Air Force Base, Delaware, 2001

USGS Publications Warehouse

Stewart, Marie; Guertal, William R.; Barbaro, Jeffrey R.; McHale, Timothy J.

2004-01-01

A joint study by the Dover National Test Site, Dover Air Force Base, Delaware, and the U.S. Geological Survey was conducted from June 27 through July 18, 2001, to determine the spatial distribution of the gasoline oxygenate additive methyl tert-butyl ether and selected water-quality constituents in the surficial aquifer underlying the Dover National Test Site. This report provides a summary assessment of the distribution of methyl tert-butyl ether and a preliminary screening of selected constituents that may affect natural attenuation and remediation demonstrations at the Dover National Test Site. The information gathered during this study is designed to assist potential remedial investigators who are considering conducting a methyl tert-butyl ether remedial demonstration at the test site. In addition, the study supported a planned enhanced bioremediation demonstration and assisted the Dover National Test Site in identifying possible locations for future methyl tert-butyl ether remediation demonstrations. A direct-push drill rig was used to collect a total of 147 ground-water samples (115 VOC samples and 32 quality-assurance samples) at varying depths. Volatile organic compounds were above the method reporting limits in 59 of the 115 ground-water samples. The concentrations ranged from below detection limits to maximum values of 12.4 micrograms per liter of cis-1,2-dichloro-ethene, 1.14 micrograms per liter of trichloro-ethene, 2.65 micrograms per liter of tetrachloro-ethene, 1,070 micrograms per liter of methyl tert-butyl ether, 4.36 micrograms per liter of benzene, and 1.8 micrograms per liter of toluene. Vinyl chloride, ethylbenzene, p,m-xylene, and o-xylene were not detected in any of the samples collected during this investigation. Methyl tert-butyl ether was detected in 47 of the 115 ground-water samples. The highest concentrations of methyl tert-butyl ether were detected in the surficial aquifer from ?4.6 to 6.4 feet mean sea level; however, methyl tert-butyl ether was detected as deep as ?9.5 feet mean sea level. Increased methane concentrations and decreased dissolved oxygen concentrations that were found in association with the ground-water samples that contained methyl tert-butyl ether are preliminary indicators that will assist in determining if natural attenuation of methyl tert-butyl ether is occurring in the surficial aquifer. A full assessment of natural attenuation of methyl tert-butyl ether at the site is beyond the scope of this study, but the data collected during the study will be useful in selecting appropriate remedial methyl tert-butyl ether demonstrations.

Yellowing reaction in encapsulant of photovoltaic modules

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

Shigekuni, T.; Kumano, M.

1997-12-31

To clarify the mechanism of the yellowing reaction in encapsulant used for photovoltaic (PV) modules, a low molecular weight substance in EVA (Ethylene vinyl acetate) under accelerated weathering test (Dew cycle test, 1000 hours) with yellow change and virgin EVA were extracted with methanol. Extracts were chemically analyzed by GCIR (Gas Chromatography Infrared-Ray spectroscopic analysis), GC-AED (Gas Chromatography Atomic Emission Detector), and FDMS (Field Desorption Mass Spectroscopy). The conditions of this accelerated test were based on JIS-K9117. The analysis results showed that 2,6-di-t-butyl-4-methyl phenol of antioxidant and 2-hydroxy-4-octoxy-benzophenone of UV absorbent were consumed after the weathering test and that 3,5-di-t-butyl-4-hydroxy-benzaldehydemore » having yellow color was newly produced. A mechanism of the yellowing reaction in encapsulant was presented here that 2,6-di-t-N-O radical from Bis-2,2,6,6-tetramethyl-4-piperidinyl sebacate to produce 3,5 di-t-butyl-4-hydroxy benzaldehyde.« less

REDUCTIVE ACTIVATION OF DIOXYGEN FOR DEGRADATION OF METHYL TERT-BUTYL ETHER BY BIFUNCTION

EPA Science Inventory

Bifunctional aluminum is prepared by sulfating aluminum metal with sulfuric acid. The use of bifunctional aluminum to degrade methyl tert-butyl ether (MTBE) in the presence of dioxygen has been examined using batch systems. Primary degradation products were tert-butyl alcohol, ...

Kinetics of proton transfer from tetra(4-nitro-5- tert-butyl)phthalocyanine to nitrogen-containing bases in benzene

NASA Astrophysics Data System (ADS)

Petrov, O. A.; Kuzmina, E. L.; Maizlish, V. E.; Rodionov, A. V.

2014-01-01

The acid-basic interaction between tetra(4-nitro-5- tert-butyl)phthalocyanine and pyridine, 2-methylpyridine, morpholine, piperidine, n-butylamine, diethylamine, and triethylamine in benzene is studied. It is found that the intermolecular transfer of protons of NH groups from tetra(4-nitro-5- tert-butyl)phthalocyanine to morpholine and diethylamine is characterized by unusually low values of the reaction constant rates. The effect of the structure of tetra(4-nitro-5- tert-butyl)phthalocyanine and tetra(3-nitro-5- tert-butyl)phthalocyanine, and of the nature of the base on the kinetic parameters of acid-base interaction is demonstrated. A structure is proposed for complexes with the transfer of displaced phthalocyanines' protons. It is found that they undergo decomposition over time.

Spin-crossover in an iron(III)-bispidine-alkylperoxide system.

PubMed

Bautz, Jochen; Comba, Peter; Que, Lawrence

2006-09-04

The iron(II) complex of a tetradentate bispidine ligand with two tertiary amines and two pyridine groups (L = dimethyl [3,7-dimethyl-9,9'-dihydroxy-2,4-di-(2-pyridyl)-3,7-diazabicyclo nonan-1,5-dicaboxylate]) is oxidized with tert-butyl hydroperoxide to the corresponding end-on tert-butylperoxo complex [Fe(III)(L)(OOtBu)(X)]n+ (X = solvent, anion). UV-vis, resonance Raman, and EPR spectroscopy, as a function of the solvent, show that this is a spin-crossover compound. The experimentally observed Raman vibrations for both low-spin and high-spin isomers are in good agreement with those computed by DFT.

Mechanism of silver-mediated di-tert-butylsilylene transfer from a silacyclopropane to an alkene.

PubMed

Driver, Tom G; Woerpel, K A

2004-08-18

Kinetic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes in the presence of 5 mol % of (Ph3P)2AgOTf suggested a possible mechanism for silver-mediated di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 was determined to be one. Inverse kinetic saturation behavior (rate inhibition) was observed in monosubstituted alkene and cyclohexene concentrations. Saturation kinetic behavior in catalyst concentration was observed. A reactive intermediate, a silylsilver complex, was observed using low temperature 29Si NMR spectroscopy. Competition experiments between substituted styrenes and a deficient amount of 1 correlated well with the Hammett equation and provided a rho value of -0.62 +/- 0.02 using sigmap constants. These data support a mechanism involving reversible silver-promoted di-tert-butylsilylene extrusion from 1 followed by irreversible concerted electrophilic attack of the silylsilver intermediate on the alkene.

Effect of oxidant stressors and phenolic antioxidants on the ochratoxigenic fungus Aspergillus carbonarius.

PubMed

Crespo-Sempere, Ana; Selma-Lázaro, Cristina; Palumbo, Jeffrey D; González-Candelas, Luis; Martínez-Culebras, Pedro V

2016-01-15

There are few studies dealing with the relationship between oxidative stress and ochratoxin A (OTA) biosynthesis. In this work, we analyzed the effect of the oxidant stressor menadione and the antioxidants 3,5-di-tert-butyl-4-hydroxytoluene (BHT), catechin, resveratrol and a polyphenolic extract on growth, generation of reactive oxygen species (ROS), OTA production and gene expression of antioxidant enzymes of Aspergillus carbonarius. Exposure to menadione concentrations higher than 20 µmol L(-1) led to increases in ROS and OTA levels and a decrease in growth rate. Exposure to 2.5-10 mmol L(-1) BHT also led to higher ROS and OTA levels, although growth rate was only affected above 5 mmol L(-1). Naturally occurring concentrations of catechin, resveratrol and polyphenolic extract barely affected growth rate, but they produced widely different effects on OTA production level depending on the antioxidant concentration used. In general, gene expression of antioxidant enzymes superoxide dismutase (SOD) and peroxiredoxin (PRX) was downregulated after exposure to oxidant and antioxidant concentrations that enhanced OTA production level. Aspergillus carbonarius responds to oxidative stress, increasing OTA production. Nevertheless, the use of naturally occurring concentrations of antioxidant phenolic compounds to reduce oxidative stress is not a valid approach by itself for OTA contamination control in grapes. © 2015 Society of Chemical Industry.

Cyclohexene oxide/CO2 copolymerization catalyzed by chromium(III) salen complexes and N-methylimidazole: effects of varying salen ligand substituents and relative cocatalyst loading.

PubMed

Darensbourg, Donald J; Mackiewicz, Ryan M; Rodgers, Jody L; Fang, Cindy C; Billodeaux, Damon R; Reibenspies, Joseph H

2004-09-20

A detailed mechanistic study into the copolymerization of CO2 and cyclohexene oxide utilizing CrIII(salen)X complexes and N-methylimidazole, where H2salen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylenediimine and other salen derivatives and X = Cl or N3, has been conducted. By studying salen ligands with various groups on the diimine backbone, we have observed that bulky groups oriented perpendicular to the salen plane reduce the activity of the catalyst significantly, while such groups oriented parallel to the salen plane do not retard copolymer formation. This is not surprising in that the mechanism for asymmetric ring opening of epoxides was found to occur in a bimetallic fashion, whereas these perpendicularly oriented groups along with the tert-butyl groups on the phenolate rings produce considerable steric requirements for the two metal centers to communicate and thus initiate the copolymerization process. It was also observed that altering the substituents on the phenolate rings of the salen ligand had a 2-fold effect, controlling both catalyst solubility as well as electron density around the metal center, producing significant effects on the rate of copolymer formation. This and other data discussed herein have led us to propose a more detailed mechanistic delineation, wherein the rate of copolymerization is dictated by two separate equilibria. The first equilibrium involves the initial second-order epoxide ring opening and is inhibited by excess amounts of cocatalyst. The second equilibrium involves the propagation step and is enhanced by excess cocatalyst. This gives the [cocatalyst] both a positive and negative effect on the overall rate of copolymerization. Copyright 2004 American Chemical Society

Identification and quantification of the migration of chemicals from plastic baby bottles used as substitutes for polycarbonate.

PubMed

Simoneau, C; Van den Eede, L; Valzacchi, S

2012-01-01

The results of a study on the analytical identification and quantification of migration of chemicals from plastics baby bottles found in the European Union market made of materials that are now present as substitutes for polycarbonate (PC) are reported. A total of 449 baby bottles with a focus on first age or sets of bottles were purchased from 26 European Union countries, Canada, Switzerland and the USA. From this collection, which contained several duplicates, a total of 277 baby bottles were analysed. The materials included different types of plastic such as PC, polyamide (PA), polyethersulphone (PES), polypropylene (PP), but also silicone, and from the United States a co-polyester marketed under the trade name Tritan™. The bottles were subjected to the conventional migration test for hot fill conditions, i.e. 2 h at 70°C. The simulant used was that specified in European Union legislation (2007/19/EC) for milk, i.e. 50% ethanol. In a first phase 1, migration was conducted since the scope of this investigation was a screening rather than a true compliance testing check. Second and third migrations were performed on selected articles when migrated substances exceeded limits specified in the legislation. In order to verify some materials, a portion of the bottle was cut to run an FT-IR fingerprint to confirm the nature of the polymer. The migration solutions in general showed a low release of substances. Results showed that bottles made of PP and silicones showed a greater number of substances in the migration solutions and in greater quantity. Chemicals from PP included alkanes, which could be found in >65% of the bottles at levels up to 3500 µg kg⁻¹; and benzene derivatives in 17% of the baby bottles and found at levels up to 113 µg kg⁻¹. Some substances were found on a regular basis such as plasticisers, esters and antioxidants (e.g. tris(2,4-di-tert-butylphenyl)phosphate, known as Irgafos 168. Some substances found were not included in the Community positive list, which means that those should not be found even in the first migration. Such substances included 2,6-di-isopropylnaphthalene (DIPN), found in 4% of the bottles at levels up to 25 µg kg⁻¹, 2,4-di-tert-butyl phenol (in 90% of the bottles at levels up 400 µg kg⁻¹). Moreover, bisphenol A (BPA) was detected and quantified in baby bottles made of PA, but limited to one brand and model specific (but labelled BPA free). Results for baby bottles made of silicone also indicated the presence of components, e.g. potentially coming from inks (benzophenone, diisopropyl naphtahalene - DIPN, which could come for example from the presence of instruction leaflets in the bottles). In the case of silicone, phthalates were also found in relevant concentrations, with levels for DiBP and DBP from the first migration test of 50-150 µg kg⁻¹ and DEHP at levels 25-50 µg kg⁻¹.

Charge and Spin States in Schiff Base Metal Complexes with a Disiloxane Unit Exhibiting a Strong Noninnocent Ligand Character: Synthesis, Structure, Spectroelectrochemistry, and Theoretical Calculations.

PubMed

Cazacu, Maria; Shova, Sergiu; Soroceanu, Alina; Machata, Peter; Bucinsky, Lukas; Breza, Martin; Rapta, Peter; Telser, Joshua; Krzystek, J; Arion, Vladimir B

2015-06-15

Mononuclear nickel(II), copper(II), and manganese(III) complexes with a noninnocent tetradentate Schiff base ligand containing a disiloxane unit were prepared in situ by reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane followed by addition of the appropriate metal(II) salt. The ligand H2L resulting from these reactions is a 2:1 condensation product of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with 1,3-bis(3-aminopropyl)tetramethyldisiloxane. The resulting metal complexes, NiL·0.5CH2Cl2, CuL·1.5H2O, and MnL(OAc)·0.15H2O, were characterized by elemental analysis, spectroscopic methods (IR, UV-vis, X-band EPR, HFEPR, (1)H NMR), ESI mass spectrometry, and single crystal X-ray diffraction. Taking into account the well-known strong stabilizing effects of tert-butyl groups in positions 3 and 5 of the aromatic ring on phenoxyl radicals, we studied the one-electron and two-electron oxidation of the compounds using both experimental (chiefly spectroelectrochemistry) and computational (DFT) techniques. The calculated spin-density distribution and localized orbitals analysis revealed the oxidation locus and the effect of the electrochemical electron transfer on the molecular structure of the complexes, while time-dependent DFT calculations helped to explain the absorption spectra of the electrochemically generated species. Hyperfine coupling constants, g-tensors, and zero-field splitting parameters have been calculated at the DFT level of theory. Finally, the CASSCF approach has been employed to theoretically explore the zero-field splitting of the S = 2 MnL(OAc) complex for comparison purposes with the DFT and experimental HFEPR results. It is found that the D parameter sign strongly depends on the metal coordination geometry.

Effect of substrate interaction on the degradation of methyl tert-butyl ether, benzene, toluene, ethylbenzene, and xylene by Rhodococcus sp.

PubMed

Lee, Eun-Hee; Cho, Kyung-Suk

2009-08-15

It was examined the substrate interactions of benzene (B), tolulene (T), ethylbenzene (E), xylene (X), and methyl tert-butyl ether (M) in binary, ternary, quaternary, and quinary mixtures by Rhodococcus sp. EH831 that could aerobically degrade all of five single components. The specific degradation rates (SDRs) of B, T, E, X, and M were 234, 913, 131, 184 and 139 micromol g-dry cell weight (DCW)(-1)h(-1), respectively. In binary, ternary, quaternary, and quinary mixtures of them, ethylbenzene was the strongest inhibitor for the other substrates, and methyl tert-butyl ether was the weakest inhibitor. Interestingly, no degradation of benzene and methyl tert-butyl ether was found in the coexistence of ethylbenzene. The degradation of benzene followed only after toluene became exhausted when both was present. Ethylbenzene was least inhibited by methyl tert-butyl ether and most inhibited by toluene.

IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) (Public Comment Draft)

EPA Science Inventory

EPA is developing an Integrated Risk Information System (IRIS) assessment of tert-butyl Alcohol (tert-butanol) and has released the public comment draft assessment for public comment and external peer review. When final, the assessment will appear on the IRIS databa...

IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) (Interagency Science Consultation Draft)

EPA Science Inventory

On April 29, 2016, the Toxicological Review of tert-Butyl Alcohol (tert-Butanol) (Public Comment Draft) was released for public comment. The draft Toxicological Review and charge were reviewed internally by EPA and by other federal agencies and the Executive Office ...

IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) (External Review Draft)

EPA Science Inventory

The IRIS Toxicological Review of tert-Butyl Alcohol (tert-Butanol) was released for external peer review in June 2017. EPA’s Science Advisory Board’s (SAB) Chemical Assessment Advisory Committee (CAAC) will conduct a peer review of the scientific basis supporting ...

Method for determination of methyl tert-butyl ether and its degradation products in water

USGS Publications Warehouse

Church, C.D.; Isabelle, L.M.; Pankow, J.F.; Rose, D.L.; Tratnyek, P.G.

1997-01-01

An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents

PubMed Central

Gau, Michael R.; Zdilla, Michael J.

2016-01-01

Organolithium reagents are powerful tools in the synthetic chemist's toolbox. However, the extreme pyrophoric nature of the most reactive reagents warrants proper technique, thorough training, and proper personal protective equipment. To aid in the training of researchers using organolithium reagents, a thorough, step-by-step protocol for the safe and effective use of tert-butyllithium on an inert gas line or within a glovebox is described. As a model reaction, preparation of lithium tert-butyl amide by the reaction of tert-butyl amine with one equivalent of tert-butyl lithium is presented. PMID:27911386

Mechanism of di-tert-butylsilylene transfer from a silacyclopropane to an alkene.

PubMed

Driver, Tom G; Woerpel, K A

2003-09-03

Kinetic and thermodynamic studies of the reactions of cyclohexene silacyclopropane 1 and monosubstituted alkenes suggested a possible mechanism for di-tert-butylsilylene transfer. The kinetic order in cyclohexene silacyclopropane 1 and cyclohexene were determined to be 1 and -1, respectively. Saturation kinetic behavior in monosubstituted alkene concentration was observed. Competition experiments between substituted styrenes and a deficient amount of di-tert-butylsilylene from 1 correlated well with the Hammett equation and provided a rho value of -0.666 +/- 0.008, using sigma(p) constants. These data supported a two-step mechanism involving reversible di-tert-butylsilylene extrusion from 1, followed by irreversible concerted electrophilic attack of the silylene on the monosubstituted alkene. Eyring activation parameters were found to be DeltaH++ = 22.1 +/- 0.9 kcal.mol(-1) and DeltaS++ = -15 +/- 2 eu. Competition experiments between cycloalkenes and allylbenzene determined cycloalkenes to be more efficient silylene traps (k(rel) =1.3, DeltaDeltaG++ = 0.200 kcal.mol(-1)). A summary of the data resulted in a postulated reaction coordinate diagram. The mechanistic studies enabled rational modification of reaction conditions that improved the synthetic utility of silylene transfer. Removal of the volatile cyclohexene from the reaction mixture into an evacuated headspace led to the formation of previously inaccessible cyclohexene-derived silacyclopropanes.

75 FR 50884 - 2-(2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole and Phenol, 2-(2H-benzotriazole-2-yl)-6...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-08-18

... 2-(2'-hydroxy-5'-methylphenyl) benzotriazole in guinea pigs showed skin sensitization; however... pesticide manufacturer. Potentially affected entities may include, but are not limited to: Crop production (NAICS code 111). Animal production (NAICS code 112). Food manufacturing (NAICS code 311). Pesticide...

Selective Formation of Secondary Amides via the Copper-Catalyzed Cross-Coupling of Alkylboronic Acids with Primary Amides

PubMed Central

Rossi, Steven A.; Shimkin, Kirk W.; Xu, Qun; Mori-Quiroz, Luis M.; Watson, Donald A.

2014-01-01

For the first time, a general catalytic procedure for the cross coupling of primary amides and alkylboronic acids is demonstrated. The key to the success of this reaction was the identification of a mild base (NaOSiMe3) and oxidant (di-tert-butyl peroxide) to promote the copper-catalyzed reaction in high yield. This transformation provides a facile, high-yielding method for the mono-alkylation of amides. PMID:23611591

Di-tert-butyl-bis(N-isopropyl-N-methyl-dithio-carbamato-κS,S')tin(IV).

PubMed

Muthalib, Amirah Faizah; Baba, Ibrahim; Samsudin, Mohd Wahid; Ng, Seik Weng

2010-03-03

The dithio-carbamate anions in the title compound, [Sn(C(4)H(9))(2)(C(5)H(10)NS(2))(2)], chelate to the Sn(IV) atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol-ecule lies across a twofold rotation axis. The crystal studied was a non-merohedral twin, the ratio of the twin components being 0.82 (1):0.18 (1).

Arylsulfotransferase from Clostridium innocuum-A new enzyme catalyst for sulfation of phenol-containing compounds.

PubMed

Mozhaev, Vadim V; Khmelnitsky, Yuri L; Sanchez-Riera, Fernando; Maurina-Brunker, Julie; Rosson, Reinhardt A; Grund, Alan D

2002-06-05

Arylsulfotransferase (AST, EC 2.8.2.22), an enzyme capable of sulfating a wide range of phenol-containing compounds was purified from a Clostridium innocuum isolate (strain 554). The enzyme has a molecular weight of 320 kDa and is composed of four subunits. Unlike many mammalian and plant arylsulfotransferases, AST from Clostridium utilizes arylsulfates, including p-nitrophenyl sulfate, as sulfate donors, and is not reactive with 3-phosphoadenosine-5'-phosphosulfate (PAPS). The enzyme possesses broad substrate specificity and is active with a variety of phenols, quinones and flavonoids, but does not utilize primary and secondary alcohols and sugars as substrates. Arylsulfotransferase tolerates the presence of 10 vol% of polar cosolvents (dimethyl formamide, acetonitrile, methanol), but loses significant activity at higher solvent concentrations of 30-40 vol%. The enzyme retains high arylsulfotransferase activity in biphasic systems composed of water and nonpolar solvents, such as cyclohexane, toluene and chloroform, while in biphasic systems with more polar solvents (ethyl acetate, 2-pentanone, methyl tert-butyl ether, and butyl acetate) the enzyme activity is completely lost. High yields of AST-catalyzed sulfation were achieved in reactions with several phenols and tyrosine-containing peptides. Overall, AST studied in this work is a promising biocatalyst in organic synthesis to afford efficient sulfation of phenolic compounds under mild reaction conditions. Copyright 2002 Wiley Periodicals, Inc. Biotechnol Bioeng 78: 567-575, 2002.

Entropy driven chain effects on ligation chemistry† †Electronic supplementary information (ESI) available: Synthetic details, applied MHKS parameters, SEC chromatograms of all samples, (HT) NMR data, experimental debonding values, SANS measurements, computational data (energy contributions and geometries in the form of Gaussian archive entries). See DOI: 10.1039/c4sc02908a Click here for additional data file.

PubMed Central

Pahnke, Kai; Brandt, Josef; Gryn'ova, Ganna; Lindner, Peter; Schweins, Ralf; Schmidt, Friedrich Georg

2015-01-01

We report the investigation of fundamental entropic chain effects that enable the tuning of modular ligation chemistry – for example dynamic Diels–Alder (DA) reactions in materials applications – not only classically via the chemistry of the applied reaction sites, but also via the physical and steric properties of the molecules that are being joined. Having a substantial impact on the reaction equilibrium of the reversible ligation chemistry, these effects are important when transferring reactions from small molecule studies to larger or other entropically very dissimilar systems. The effects on the DA equilibrium and thus the temperature dependent degree of debonding (%debond) of different cyclopentadienyl (di-)functional poly(meth-)acrylate backbones (poly(methyl methacrylate), poly(iso-butyl methacrylate), poly(tert-butyl methacrylate), poly(iso-butyl acrylate), poly(n-butyl acrylate), poly(tert-butyl acrylate), poly(methyl acrylate) and poly(isobornyl acrylate)), linked via a difunctional cyanodithioester (CDTE) were examined via high temperature (HT) NMR spectroscopy as well as temperature dependent (TD) SEC measurements. A significant impact of not only chain mass and length with a difference in the degree of debonding of up to 30% for different lengths of macromonomers of the same polymer type but – remarkably – as well the chain stiffness with a difference in bonding degrees of nearly 20% for isomeric poly(butyl acrylates) is found. The results were predicted, reproduced and interpreted via quantum chemical calculations, leading to a better understanding of the underlying entropic principles. PMID:29560194

IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) ...

EPA Pesticide Factsheets

The IRIS Toxicological Review of tert-Butyl Alcohol (tert-Butanol) was released for external peer review in June 2017. EPA’s Science Advisory Board’s (SAB) Chemical Assessment Advisory Committee (CAAC) will conduct a peer review of the scientific basis supporting the tert-butanol assessment and release a final report of their review. Information regarding the peer review can be found on the SAB website. EPA is conducting an Integrated Risk Information System (IRIS) health assessment for tert-butanol. The outcome of this project is a Toxicological Review and IRIS Summary for tert-butanol that will be entered into the IRIS database.

The lightest organic radical cation for charge storage in redox flow batteries

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

Huang, Jinhua; Pan, Baofei; Duan, Wentao

2016-08-25

Electrochemically reversible fluids of high energy density are promising materials for capturing the electrical energy generated from intermittent sources like solar and wind. To meet this technological challenge there is a need to understand the fundamental limits and interplay of electrochemical potential, stability and solubility in “lean” derivatives of redox-active molecules. Here we describe the process of molecular pruning, illustrated for 2,5-di-tert-butyl-1,4-bis(2-methoxyethoxy)benzene, a molecule known to produce a persistently stable, high-potential radical cation. By systematically shedding molecular fragments considered important for radical cation steric stabilization, we discovered a minimalistic structure that retains long-term stability in its oxidized form. Interestingly, wemore » find the tert-butyl groups are unnecessary; high stability of the radical cation and high solubility are both realized in derivatives having appropriately positioned arene methyl groups. These stability trends are rationalized by mechanistic considerations of the postulated decomposition pathways. We suggest that the molecular pruning approach will uncover lean redox active derivatives for electrochemical energy storage leading to materials with long-term stability and high intrinsic capacity.« less

Identification of tert-Butyl Cations in Zeolite H-ZSM-5: Evidence from NMR Spectroscopy and DFT Calculations.

PubMed

Dai, Weili; Wang, Chuanming; Yi, Xianfeng; Zheng, Anmin; Li, Landong; Wu, Guangjun; Guan, Naijia; Xie, Zaiku; Dyballa, Michael; Hunger, Michael

2015-07-20

Experimental evidence for the presence of tert-butyl cations, which are important intermediates in acid-catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with (1)H/(13)C magic-angle-spinning NMR spectroscopy, the tert-butyl cation was successfully identified on zeolite H-ZSM-5 upon conversion of isobutene by capturing this intermediate with ammonia. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analytical results from ground-water sampling using a direct-push technique at the Dover National Test Site, Dover Air Force Base, Delaware, June-July 2001

USGS Publications Warehouse

Guertal, William R.; Stewart, Marie; Barbaro, Jeffrey R.; McHale, Timthoy J.

2004-01-01

A joint study by the Dover National Test Site and the U.S. Geological Survey was conducted from June 27 through July 18, 2001 to determine the spatial distribution of the gasoline oxygenate additive methyl tert-butyl ether and selected water-quality constituents in the surficial aquifer underlying the Dover National Test Site at Dover Air Force Base, Delaware. The study was conducted to support a planned enhanced bio-remediation demonstration and to assist the Dover National Test Site in identifying possible locations for future methyl tert-butyl ether remediation demonstrations. This report presents the analytical results from ground-water samples collected during the direct-push ground-water sampling study. A direct-push drill rig was used to quickly collect 115 ground-water samples over a large area at varying depths. The ground-water samples and associated quality-control samples were analyzed for volatile organic compounds and methyl tert-butyl ether by the Dover National Test Site analytical laboratory. Volatile organic compounds were above the method reporting limits in 59 of the 115 ground-water samples. The concentrations ranged from below detection limits to maximum values of 12.4 micrograms per liter of cis-1,2-dichloroethene, 1.14 micrograms per liter of trichloroethene, 2.65 micrograms per liter of tetrachloroethene, 1,070 micrograms per liter of methyl tert-butyl ether, 4.36 micrograms per liter of benzene, and 1.8 micrograms per liter of toluene. Vinyl chloride, ethylbenzene, p,m-xylene, and o-xylene were not detected in any of the samples collected during this investigation. Methyl tert-butyl ether was detected in 47 of the 115 ground-water samples. The highest methyl tert-butyl ether concentrations were found in the surficial aquifer from -4.6 to 6.4 feet mean sea level, however, methyl tert-butyl ether was detected as deep as -9.5 feet mean sea level. Increased methane concentrations and decreased dissolved oxygen concentrations were found in samples that contained methyl tert-butyl ether.

Chiral recognition by formation of paramagnetic diastereomeric complexes

NASA Astrophysics Data System (ADS)

Scheffler, K.; Höfler, U.; Schuler, P.; Stegmann, H. B.

The chiral 4-(α-hydroxy-benzyl)-2,6-di-tert. butyl-phenoxyl has been examined in its racemic form in toluene and carbontetrachloride. On adding of chiral auxiliaries (R)-resp. (S)-N,N-dimethyl-1-phenylethylamine or (S)-phenylethyl-amine two different couplings of the β-proton are recorded by ENDOR spectroscopy. The experimental results are interpreted by a ternary equilibrium between radical, solvent and auxiliary. A model for the suggested association processes is given and equilibrium constants and corresponding enthalpies are calculated.

Interfacing an aspiration ion mobility spectrometer to a triple quadrupole mass spectrometer

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

Adamov, Alexey; Viidanoja, Jyrki; Kaerpaenoja, Esko

2007-04-15

This article presents the combination of an aspiration-type ion mobility spectrometer with a mass spectrometer. The interface between the aspiration ion mobility spectrometer and the mass spectrometer was designed to allow for quick mounting of the aspiration ion mobility spectrometer onto a Sciex API-300 triple quadrupole mass spectrometer. The developed instrumentation is used for gathering fundamental information on aspiration ion mobility spectrometry. Performance of the instrument is demonstrated using 2,6-di-tert-butyl pyridine and dimethyl methylphosphonate.

Di-tert-butyl­bis(N-isopropyl-N-methyl­dithio­carbamato-κ2 S,S′)tin(IV)

PubMed Central

Muthalib, Amirah Faizah; Baba, Ibrahim; Samsudin, Mohd Wahid; Ng, Seik Weng

2010-01-01

The dithio­carbamate anions in the title compound, [Sn(C4H9)2(C5H10NS2)2], chelate to the SnIV atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol­ecule lies across a twofold rotation axis. The crystal studied was a non-merohedral twin, the ratio of the twin components being 0.82 (1):0.18 (1). PMID:21580471

A series of (E)-5-(arylideneamino)-1-tert-butyl-1H-pyrrole-3-carbonitriles and their reduction products to secondary amines: syntheses and X-ray structural studies.

PubMed

Macías, Mario A; Castillo, Juan Carlos; Portilla, Jaime

2018-01-01

An efficent access to a series of N-(pyrrol-2-yl)amines, namely (E)-1-tert-butyl-5-[(4-chlorobenzylidene)amino]-1H-pyrrole-3-carbonitrile, C 16 H 16 ClN 3 , (7a), (E)-1-tert-butyl-5-[(2,4-dichlorobenzylidene)amino]-1H-pyrrole-3-carbonitrile, C 16 H 15 Cl 2 N 3 , (7b), (E)-1-tert-butyl-5-[(pyridin-4-ylmethylene)amino]-1H-pyrrole-3-carbonitrile, C 15 H 16 N 4 , (7c), 1-tert-butyl-5-[(4-chlorobenzyl)amino]-1H-pyrrole-3-carbonitrile, C 16 H 18 ClN 3 , (8a), and 1-tert-butyl-5-[(2,4-dichlorobenzyl)amino]-1H-pyrrole-3-carbonitrile, C 16 H 17 Cl 2 N 3 , (8b), by a two-step synthesis sequence (solvent-free condensation and reduction) starting from 5-amino-1-tert-butyl-1H-pyrrole-3-carbonitrile is described. The syntheses proceed via isolated N-(pyrrol-2-yl)imines, which are also key synthetic intermediates of other valuable compounds. The crystal structures of the reduced compounds showed a reduction in the symmetry compared with the corresponding precursors, viz. Pbcm to P-1 from compound (7a) to (8a) and P2 1 /c to P-1 from compound (7b) to (8b), probably due to a severe change in the molecular conformations, resulting in the loss of planarity observed in the nonreduced compounds. In all of the crystals, the supramolecular assembly is controlled mainly by strong (N,C)-H...N hydrogen bonds. However, in the case of (7a)-(7c), C-H...Cl interactions are strong enough to help in the three-dimensional architecture, as observed in Hirshfeld surface maps.

Dissolution DNP-NMR spectroscopy using galvinoxyl as a polarizing agent

NASA Astrophysics Data System (ADS)

Lumata, Lloyd L.; Merritt, Matthew E.; Malloy, Craig R.; Sherry, A. Dean; van Tol, Johan; Song, Likai; Kovacs, Zoltan

2013-02-01

The goal of this work was to test feasibility of using galvinoxyl (2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy) as a polarizing agent for dissolution dynamic nuclear polarization (DNP) NMR spectroscopy. We have found that galvinoxyl is reasonably soluble in ethyl acetate, chloroform, or acetone and the solutions formed good glasses when mixed together or with other solvents such as dimethyl sulfoxide. W-band electron spin resonance (ESR) measurements revealed that galvinoxyl has an ESR linewidth D intermediate between that of carbon-centered free radical trityl OX063 and the nitroxide-based 4-oxo-TEMPO, thus the DNP with galvinoxyl for nuclei with low gyromagnetic ratio γ such as 13C and 15N is expected to proceed predominantly via the thermal mixing process. The optimum radical concentration that would afford the highest 13C nuclear polarization (approximately 6% for [1-13C]ethyl acetate) at 3.35 T and 1.4 K was found to be around 40 mM. After dissolution, large liquid-state NMR enhancements were achieved for a number of 13C and 15N compounds with long spin-lattice relaxation time T1. In addition, the hydrophobic galvinoxyl free radical can be easily filtered out from the dissolution liquid when water is used as the solvent. These results indicate that galvinoxyl can be considered as an easily available free radical polarizing agent for routine dissolution DNP-NMR spectroscopy.

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

Inbar, S.; Linschitz, H.; Cohen, S.G.

Nanosecond flash photolysis, steady irradiation, and deuterium substitution studies have been carried out on solutions of benzophenone with added reductants. Quantum yields (phi/sub ketyl/) for reduction in benzene of benzophenone triplet to ketyl radical, based on phi = 2 for benzhydrol (I), were approx. 1 for cyclohexane (II), tert-butylamine (III), 2-aminobutane (IV), cyclohexylamine (V), di-n-propylamine (VI), and triethylamine (VII), approx. 0.7 for 1,4-diazabicyclo(2.2.2)octane (VIII), and approx. 0 for tert-butyl alcohol (IX). Thus, quenching, without radical formation by H abstraction from N and/or ..cap alpha..-C, does not occur with common aliphatic amines but does with Dabco (VIII). The latter quenching ismore » markedly increased by small additions of acetonitrile; the flash spectrum from this compound indicates formation of a triplet amine CT complex or radical ion pair. Triplet-reductant interaction rate constants, k/sur ir/, are high for the amines (approx. 10/sup 8/-10/sup 9/ M/sup -1/ s/sup -1/) but also show significant deuterium kinetic isotope effects: 1.9 with III-N-d/sub 2/; 1.4 with IV-N-d/sub 2/; 1.2-1.3 with IV-..cap alpha..-C-d. It is proposed that k/sub ir/ measures H atom abstraction, favored in the transition state by an initial charge-transfer interaction. Overall steady irradiation quantum yields of reduction by amines, phi/sub Red/, are much lower than phi/sub ketyl/. This is attributed to disproportionationreactions of ketyl and alkylaminyl radicals for primary and secondary amines, and, possibly, aminoalkyl radicals for tertiary amines. In the case of tert-butylamine, the rate constant for disproportionation is obtained from the decay kinetics of ketyl radical and leads to phi/sub Red/ in agreement with that directly measured.« less

The Synthesis and Isolation of N-Tert-Butyl-2-Phenylsuccinamic Acid and N-Tert-Butyl-3-Phenylsuccinamic Acid: An Undergraduate Organic Chemistry Laboratory Experiment

ERIC Educational Resources Information Center

Cesare, Victor; Sadarangani, Ishwar; Rollins, Janet; Costello, Dennis

2004-01-01

The facile, high yielding synthesis of phenylsuccinamic acids is described and one of these syntheses, the reaction of phenylsuccinic anhydride with tert-butylamine, is successfully modified and adapted for use in the second-semester organic chemistry laboratory at St. John's University. Succinamic acids are compounds that contain both the amide…

Aerobic mineralization of MTBE and tert-butyl alcohol by stream-bed sediment microorganisms

USGS Publications Warehouse

Bradley, P.M.; Landmeyer, J.E.; Chapelle, F.H.

1999-01-01

Microorganisms indigenous to the stream-bed sediments at two gasoline- contaminated groundwater sites demonstrated significant mineralization of the fuel oxygenates, methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA). Up to 73% of [U-14C]-MTBE and 84% of [U-14C]-TBA were degraded to 14CO2 under mixed aerobic/anaerobic conditions. No significant mineralization was observed under strictly anaerobic conditions. The results indicate that, under the mixed aerobic/anaerobic conditions characteristic of stream-bed sediments, microbial processes may provide a significant environmental sink for MTBE and TBA delivered to surface water bodies by contaminated groundwater or by other sources.Microorganisms indigenous to the stream-bed sediments at two gasoline-contaminated groundwater sites demonstrated significant mineralization of the fuel oxygenates, methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA). Up to 73% of [U-14C]-MTBE and 84% of [U-14C]-TBA were degraded to 14CO2 under mixed aerobic/anaerobic conditions. No significant mineralization was observed under strictly anaerobic conditions. The results indicate that, under the mixed aerobic/anaerobic conditions characteristic of stream-bed sediments, microbial processes may provide a significant environmental sink for MTBE and TBA delivered to surface water bodies by contaminated groundwater or by other sources.

Gastroprotective Activity of Ethyl-4-[(3,5-di-tert-butyl-2-hydroxybenzylidene) Amino]benzoate against Ethanol-Induced Gastric Mucosal Ulcer in Rats

PubMed Central

Halabi, Mohammed Farouq; Shakir, Raied Mustafa; Bardi, Daleya Abdulaziz; Al-Wajeeh, Nahla Saeed; Ablat, Abdulwali; Hassandarvish, Pouya; Hajrezaie, Maryam; Norazit, Anwar; Abdulla, Mahmood Ameen

2014-01-01

Background The study was carried out to determine the cytotoxic, antioxidant and gastro-protective effect of ethyl-4-[(3,5-di-tert-butyl-2-hydroxybenzylid ene)amino] benzoate (ETHAB) in rats. Methodology/Principal Findings The cytotoxic effect of ETHAB was assessed using a MTT cleavage assay on a WRL68 cell line, while its antioxidant activity was evaluated in vitro. In the anti-ulcer study, rats were divided into six groups. Group 1 and group 2 received 10% Tween 20 (vehicle). Group 3 received 20 mg/kg Omeprazole. Groups 4, 5 and 6 received ETHAB at doses of 5, 10, and 20 mg/kg, respectively. After an hour, group 1 received the vehicle. Groups 2–6 received absolute ethanol to induce gastric mucosal lesions. In the WRL68 cell line, an IC50 of more than 100 µg/mL was observed. ETHAB results showed antioxidant activity in the DPPH, FRAP, nitric oxide and metal chelating assays. There was no acute toxicity even at the highest dosage (1000 mg/kg). Microscopy showed that rats pretreated with ETHAB revealed protection of gastric mucosa as ascertained by significant increases in superoxide dismutase (SOD), pH level, mucus secretion, reduced gastric lesions, malondialdehyde (MDA) level and remarkable flattened gastric mucosa. Histologically, pretreatment with ETHAB resulted in comparatively better gastric protection, due to reduction of submucosal edema with leucocyte infiltration. PAS staining showed increased intensity in uptake of Alcian blue. In terms of immunohistochemistry, ETHAB showed down-expression of Bax proteins and over-expression of Hsp70 proteins. Conclusion/Significance The gastroprotective effect of ETHAB may be attributed to antioxidant activity, increased gastric wall mucus, pH level of gastric contents, SOD activity, decrease in MDA level, ulcer area, flattening of gastric mucosa, reduction of edema and leucocyte infiltration of the submucosal layer, increased PAS staining, up-regulation of Hsp70 protein and suppressed expression of Bax. Key words: ethyl 4-(3, 5-di-ter-butyl-2-hydroxybenzylamino) benzoate; toxicity; antioxidant; gastric-ulcer; anti-ulcer; histology; immunohistochemistry. PMID:24800807

Methyl tert-butyl ether (MTBE)

Integrated Risk Information System (IRIS)

Methyl tert - butyl ether ( MTBE ) ; CASRN 1634 - 04 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

Vapor intrusion risk of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME) and ethyl tert-butyl ether (ETBE): A modeling study.

PubMed

Ma, Jie; Xiong, Desen; Li, Haiyan; Ding, Yi; Xia, Xiangcheng; Yang, Yongqi

2017-06-15

Vapor intrusion of synthetic fuel additives represents a critical yet still neglected problem at sites contaminated by petroleum fuel releases. This study used an advanced numerical model to investigate the vapor intrusion potential of fuel ether oxygenates methyl tert-butyl ether (MTBE), tert-amyl methyl ether (TAME), and ethyl tert-butyl ether (ETBE). Simulated indoor air concentration of these compounds can exceed USEPA indoor air screening level for MTBE (110μg/m 3 ). Our results also reveal that MTBE has much higher chance to cause vapor intrusion problems than TAME and ETBE. This study supports the statements made by USEPA in the Petroleum Vapor Intrusion (PVI) Guidance that the vertical screening criteria for petroleum hydrocarbons may not provide sufficient protectiveness for fuel additives, and ether oxygenates in particular. In addition to adverse impacts on human health, ether oxygenate vapor intrusion may also cause aesthetic problems (i.e., odour and flavour). Overall, this study points out that ether oxygenates can cause vapor intrusion problems. We recommend that USEPA consider including the field measurement data of synthetic fuel additives in the existing PVI database and possibly revising the PVI Guidance as necessary. Copyright © 2017 Elsevier B.V. All rights reserved.

PHOTOCATALYTIC OXIDATION OF METHYL-TERT-BUTYL ETHER FOR DRINKING WATER TREATMENT

EPA Science Inventory

The photo-oxidation of methyl tert-butyl ether (MTBE) in water was investigated to determine the feasibility of using photocatalysis for the treatment of MTBE-contaminated drinking water. The feasibility assessment was conducted using slurries of titanium dioxide in both a photo-...

Light-Induced C-H Arylation of (Hetero)arenes by In Situ Generated Diazo Anhydrides.

PubMed

Cantillo, David; Mateos, Carlos; Rincon, Juan A; de Frutos, Oscar; Kappe, C Oliver

2015-09-07

Diazo anhydrides (Ar-N=N-O-N=N-Ar) have been known since 1896 but have rarely been used in synthesis. This communication describes the development of a photochemical catalyst-free C-H arylation methodology for the preparation of bi(hetero)aryls by the one-pot reaction of anilines with tert-butyl nitrite and (hetero)arenes under neutral conditions. The key step in this procedure is the in situ formation and subsequent photochemical (>300 nm) homolytic cleavage of a transient diazo anhydride intermediate. The generated aryl radical then efficiently reacts with a (hetero)arene to form the desired bi(hetero)aryls producing only nitrogen, water, and tert-butanol as byproducts. The scope of the reaction for several substituted anilines and (hetero)arenes was investigated. A continuous-flow protocol increasing selectivity and safety has been developed enabling the experimentally straightforward preparation of a variety of substituted bi(hetero)aryls within 45 min of reaction time. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

EVALUATION OF METHYL TERT-BUTYL ETHER (MTBE) AS AN INTERFERENCE ON COMMERCIAL BREATH-ALCOHOL ANALYZERS

EPA Science Inventory

Anecdotal reports suggest that high environmental or occupational exposures to the fuel oxygenate methyl tert-butyl ether (MTBE) may result in breath concentrations that are sufficiently elevated to cause a false positive on commercial breath-alcohol analyzers. We evaluated th...

BIODEGRADATION OF METHYL TERT-BUTYL ETHER AND BTEX AT VARYING HYDRAULIC RETENTION TIMES

EPA Science Inventory

The feasibility of biologically degrading methyl tert-butyl ether (MTBE) contaminated groundwater is dependent on the ability to degrade MTBE and its byproducts in the presence of other gasoline contaminants. This study investigates a mixed culture degrading both MTBE and benzene...

Temperature effect on tert-butyl alcohol (TBA) biodegradation kinetics in hyporheic zone soils.

PubMed

Greenwood, Mark H; Sims, Ronald C; McLean, Joan E; Doucette, William J

2007-09-19

Remediation of tert-butyl alcohol (TBA) in subsurface waters should be taken into consideration at reformulated gasoline contaminated sites since it is a biodegradation intermediate of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-butyl formate (TBF). The effect of temperature on TBA biodegradation has not been not been published in the literature. Biodegradation of [U 14C] TBA was determined using hyporheic zone soil microcosms. First order mineralization rate constants of TBA at 5 degrees C, 15 degrees C and 25 degrees C were 7.84 +/- 0.14 x 10-3, 9.07 +/- 0.09 x 10-3, and 15.3 +/- 0.3 x 10-3 days-1, respectively (or 2.86 +/- 0.05, 3.31 +/- 0.03, 5.60 +/- 0.14 years-1, respectively). Temperature had a statistically significant effect on the mineralization rates and was modelled using the Arrhenius equation with frequency factor (A) and activation energy (Ea) of 154 day-1 and 23,006 mol/J, respectively. Results of this study are the first to determine mineralization rates of TBA for different temperatures. The kinetic rates determined in this study can be used in groundwater fate and transport modelling of TBA at the Ronan, MT site and provide an estimate for TBA removal at other similar shallow aquifer sites and hyporheic zones as a function of seasonal change in temperature.

BIODEGRADATION OF METHYL TERT-BUTYL ETHER USING AN INNOVATIVE BIOMASS CONCENTRATOR REACTOR

EPA Science Inventory

The aerobic biodegradation of methyl tert-butyl ether (MTBE) was investigated using a pilot-scale Biomass Concentrator Reactor (BCR). The reactor was operated for a year at a flow rate of 2500 L/d of Cincinnati dechlorinated tap water and an influent MTBE concentration o...

TREATMENT OF METHYL TERT-BUTYL ETHER CONTAMINATED WATER USING PHOTOCATALYSIS

EPA Science Inventory

The feasibility of photo-oxidation treatment of methyl tert-butyl ether (MTBE) in water was investigated in three ways, 1) using a slurry falling film photo-reactor, 2) a batch solar reactor system, and 3) a combination of air-stripping and gas phase photooxidation system. MTBE-c...

STRUCTURES AND BINDING ENERGIES OF METHYL TERT-BUTYL ETHER-WATER COMPLEXES

EPA Science Inventory

Methyl tert-butyl ether (MTBE) is a well-known environmental contaminant owing to its high solubility in water. Since the early 1990s, MTBE has been added to gasoline to improve air quality in some metropolitan areas of the United States. Improved air quality was, however, achiev...

Estrogenic activities of chemicals related to food contact plastics and rubbers tested by the yeast two-hybrid assay.

PubMed

Ogawa, Yuko; Kawamura, Yoko; Wakui, Chiseko; Mutsuga, Motoh; Nishimura, Tetsuji; Tanamoto, Kenichi

2006-04-01

Food contact plastics and rubbers possibly contain many kinds of chemicals such as monomers, oligomers, additives, degradation products of polymers and additives, and impurities. Among them, bisphenol A, nonylphenol, benzylbutyl phthalate, styrene oligomers and hydroxylated benzophenones have been reported to possess estrogenic activities. In this study, other chemicals related to food contact plastics and rubbers, and their metabolites induced by the S9-mixture were tested for their estrogenic activities using the yeast two-hybrid assay. Among the 150 chemicals, 10 chemicals such as bis(4-hydroxyphenyl) methane, 4-cyclohexylphenol, 4-phenylphenol, 4,4'-isopropylidenediphenol alkylphosphite, two type of styrenated phenol (including mono type), tris(nonylphenyl) phosphite, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2,4-diphenyl-4-methyl-1-pentene, their metabolites and the metabolites of 6 other chemicals, such as 2-(phenylmethyl) phenol, styrenated phenol (di and tri type), 1-(N-phenylamino)naphthalene, 4-tert-butylphenylsalicylate, nonylphenol ethoxylates and 2-methyl-6-tert-butylphenol, displayed estrogenic activities. All of them contained a phenol group in their chemical structures or formed one easily by hydrolysis or metabolism. However, most of the chemicals related to food contact plastics and rubbers, and their metabolites did not show any estrogenicity.

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism

PubMed Central

Kyong, Jin Burm; Lee, Yelin; D’Souza, Malcolm John; Kevill, Dennis Neil; Kevill, Dennis Neil

2012-01-01

The “parent” tertiary alkyl chloroformate, tert-butyl chloroformate, is unstable, but the tert-butyl chlorothioformate (1) is of increased stability and a kinetic investigation of the solvolyses is presented. Analyses in terms of the simple and extended Grunwald-Winstein equations are carried out. The original one-term equation satisfactorily correlates the data with a sensitivity towards changes in solvent ionizing power of 0.73 ±0.03. When the two-term equation is applied, the sensitivity towards changes in solvent nucleophilicity of 0.13 ± 0.09 is associated with a high (0.17) probability that the term that it governs is not statistically significant. PMID:23538747

Purification of dirucotide, a synthetic 17-aminoacid peptide, by ion exchange centrifugal partition chromatography.

PubMed

Boudesocque, Leslie; Forni, Luciano; Martinez, Agathe; Nuzillard, Jean-Marc; Giraud, Matthieu; Renault, Jean-Hugues

2017-09-01

Dirucotide is a synthetic drug candidate for the treatment of multiple sclerosis. This 17-aminoacid peptide was successfully purified by ion exchange centrifugal partition chromatography. The optimized conditions involved the biphasic methyl tert-butyl ether/acetonitrile/n-butanol/water (2:1:2:5, v/v) solvent system in the descending mode, the di(2-ethylhexyl)phosphoric acid cation-exchanger with an exchanger (di(2-ethylhexyl)phosphoric acid)/dirucotide mole ratio of 100 and Ca 2+ ions in aqueous solution as displacer. Critical impurities were efficiently eliminated and dirucotide was recovered in high yield and purity (69% and 98%, respectively) and with a productivity of 2.29g per liter of stationary phase per hour. Copyright © 2017 Elsevier B.V. All rights reserved.

Treatment Of Groundwater Contaminated With PAHs, Gasoline Hydrocarbons, And Methyl Tert-Butyl Ether In A Laboratory Biomass-Retaining Bioreactor

EPA Science Inventory

In this study, we investigated the treatability of co-mingled groundwater contaminated with polycyclic aromatic hydrocarbons (PAHs), gasoline hydrocarbons, and methyl tert-butyl ether (MtBE) using an ex-situ aerobic biotreatment system. The PAHs of interest were nap...

Anaerobic Biodegradation Of Methyl tert-Butyl Ether Under Iron-Reducing Conditions In Batch And Continuous-Flow Cultures

EPA Science Inventory

The feasibility of biodegradation of the fuel oxygenate methyl tert-butyl ether (MTBE) under iron-reducing conditions was explored in batch and continuous-flow systems. A porous pot completely-mixed reactor was seeded with diverse cultures and operated under iron-reducing...

INFLUENCE OF METHYL TERT-BUTYL ETHER (MTBE) ON LAKE WATER ALGAE

EPA Science Inventory

Methyl tert-butyl ether (MTBE) has been used as an octane booster in gasoline in the United States since the 1970s. MTBE use increased greatly in the 1990s with the implementation of the Clean Air Act Amendments of 1990. The MTBE enhanced a more complete combustion of fuel hydroc...

ATTENUATION OF METHYL TERT-BUTYL ETHER IN WATER USING SUNLIGHT AND A PHOTOCATALYST

EPA Science Inventory

The use of methyl tert-butyl ether (MTBE) as a gasoline additive has resulted in increasing pollution of ground water. Most of the conventional treatment technologies are inefficient or costly when the initial concentration of MTBE is low (<200 ug/L). In order to find an eco-frie...

ANAEROBIC DEGRADATION OF MTBE TO TBA IN GROUND WATER AT GASOLINE SPILL SITES IN ORANGE COUNTY, CALIFORNIA

EPA Science Inventory

Although tert-Butyl Alcohol (TBA) has not been used as a fuel oxygenate in Orange County, California, the concentrations of TBA in ground water at gasoline spill sites are high compared to the concentrations of the conventional fuel oxygenate Methyl tert-Butyl Ether (MTBE). In t...

STABLE ISOTOPE ANALYSIS OF MTBE TO EVALUATE THE SOURCE OF TBA IN GROUND WATER

EPA Science Inventory

Although tert-butyl alcohol (TBA) has not been used as a fuel oxygenate in Orange County, California, the concentrations of TBA in ground water at gasoline spill sites are high compared those of the conventional fuel oxygenate methyl tert-butyl ether (MTBE). In the year 2002, th...

CO-OCCURRENCE OF METHYL- TERT-BUTYL ETHER (MTBE) AND BTEX COMPOUNDS AT MARINAS IN A LARGE RESEVOIR

EPA Science Inventory

Methyl tert-butyl ether (MTBE) is released into the environment as one of some gasoline components, not as a pure compound. BTEX compounds (benzene, tolune, ethylbenzene, and xylenes) are major volatile constituents found in gasoline and are water soluble and mobile. This study...

INHALATION EXPOSURE TO METHYL TERT-BUTYL ETHER (MTBE) AND DIBROMOCHLOROMETHANE (DBCM) USING CONTINUOUS BREATH ANALYSIS

EPA Science Inventory

The oxygenate methyl tert-butyl ether (MTBE) has been added to gasoline to help meet national ambient air quality standards in those parts of the U.S. that are non-compliant for carbon monoxide. Although MTBE has provided important health benefits in terms of reduced haza...

DERMAL EXPOSURE TO METHYL TERT-BUTYL ETHER (MTBE) AND DIBROMOCHLOROMETHANE (DBCM) WHILE BATHING WITH CONTAMINATED WATER

EPA Science Inventory

The oxygenate methyl tert-butyl ether (MTBE) has been added to gasoline to help meet national ambient air quality standards in those parts of the U.S. that are non-compliant for carbon monoxide. Although MTBE has provided important health benefits in terms of reduced hazardous a...

OCCURRENCE OF METYL TERT-BUTYL ETHER (MTBE) AT FIVE MARINAS IN LAKE TEXOMA

EPA Science Inventory

Occurrence of methyl tert-butyl ether (MTBE) in five marinas was monitored between June 1999 and November 2000 in Lake Texoma located on the border of Oklahoma and Texas. MTBE is a commonly used gasoline additive and a suspected carcinogen. Lake water was collected at loc...

WATER QUALITY AT FIVE MARINAS IN LAKE TEXOMA AS RELATED TO METHYL TERT-BUTYL ETHER (MTBE)

EPA Science Inventory

Occurrence of methyl tert-butyl ether (MTBE) in five marinas was monitored between June 1999 and November 2000 in Lake Texoma located on the border of Oklahoma and Texas. MTBE is a commonly used gasoline additive and a suspected carcinogen. Lake water was collected at locations i...

Synthesis and characterization of novel chiral ionic liquids and investigation of their enantiomeric recognition properties.

PubMed

Bwambok, David K; Marwani, Hadi M; Fernand, Vivian E; Fakayode, Sayo O; Lowry, Mark; Negulescu, Ioan; Strongin, Robert M; Warner, Isiah M

2008-02-01

We report the synthesis and characterization of amino acid ester based chiral ionic liquids, derived from L- and D-alanine tert butyl ester chloride. The synthesis was accomplished via an anion metathesis reaction between commercially available L- and D-alanine tert butyl ester chloride using a variety of counterions such as lithium bis (trifluoromethane) sulfonimide, silver nitrate, silver lactate, and silver tetrafluoroborate. Both enantiomeric forms were obtained as confirmed by bands of opposite sign in the circular dichroism spectra. The L- and D-alanine tert butyl ester bis (trifluoromethane) sulfonimide were obtained as liquids at room temperature and intriguingly exhibited the highest thermal stability (up to 263 degrees C). In addition, the ionic liquids demonstrated enantiomeric recognition ability as evidenced by splitting of racemic Mosher's sodium salt signal using a liquid state (19)F nuclear magnetic resonance (NMR) and fluorescence spectroscopy. The L- and D-alanine tert butyl ester chloride resulted in solid salts with nitrate, lactate, and tetrafluoroborate anions. This illustrates the previously observed tunability of ionic liquid synthesis, resulting in ionic liquids of varying properties as a function of varying the anion.

Aqueous solubilities of alkylphenols and methoxyphenols at 25 C

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

Varhanickova, D.; Shiu, W.Y.; Mackay, D.

1995-03-01

The aqueous solubilities of 25 phenolic substances (2-methylphenol; 3-methylphenol; 4-methylphenol; 2,3-dimethylphenol; 2,4-dimethylphenol; 2,5-dimethylphenol; 2,6-dimethylphenol; 3,4-dimethylphenol; 3,5dimethylphenol; 2-ethylphenol: 4-ethylphenol; 2,3,5-trimethylphenol; 2,4,6-trimethylphenol; 3,4,5-trimethylphenol; 4-propylphenol; 2-isopropylphenol; 4-isopropylphenol; 4-butylphenol; 3-tert-butylphenol; 4-tert-butylphenol; 4-hexylphenol; 3,5-di-tert-butylphenol; 4-octylphenol; 3-methoxyphenol; and 4-methoxyphenol) were determined at 25 C, by a conventional shake-flask, batch contacting method with analysis by high-pressure liquid chromatography with LTV detection. Satisfactory agreement was obtained between measured and previously reported solubilities for 10 of these substances. The liquid or supercooled liquid solubilities are satisfactorily correlated with the solute`s LeBas molar volume and with first-order valence molecular connectivity, yielding structure-property relationships that may be useful for predictive purposes.

Temperature effect on tert-butyl alcohol (TBA) biodegradation kinetics in hyporheic zone soils

PubMed Central

Greenwood, Mark H; Sims, Ronald C; McLean, Joan E; Doucette, William J

2007-01-01

Background Remediation of tert-butyl alcohol (TBA) in subsurface waters should be taken into consideration at reformulated gasoline contaminated sites since it is a biodegradation intermediate of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-butyl formate (TBF). The effect of temperature on TBA biodegradation has not been not been published in the literature. Methods Biodegradation of [U 14C] TBA was determined using hyporheic zone soil microcosms. Results First order mineralization rate constants of TBA at 5°C, 15°C and 25°C were 7.84 ± 0.14 × 10-3, 9.07 ± 0.09 × 10-3, and 15.3 ± 0.3 × 10-3 days-1, respectively (or 2.86 ± 0.05, 3.31 ± 0.03, 5.60 ± 0.14 years-1, respectively). Temperature had a statistically significant effect on the mineralization rates and was modelled using the Arrhenius equation with frequency factor (A) and activation energy (Ea) of 154 day-1 and 23,006 mol/J, respectively. Conclusion Results of this study are the first to determine mineralization rates of TBA for different temperatures. The kinetic rates determined in this study can be used in groundwater fate and transport modelling of TBA at the Ronan, MT site and provide an estimate for TBA removal at other similar shallow aquifer sites and hyporheic zones as a function of seasonal change in temperature. PMID:17877835

Novel types of tetra-, hexa-, octa-, and dodecanuclear silver clusters containing (2,7-Di-tert-butylfluoren-9-ylidene)methanedithiolate.

PubMed

Vicente, José; González-Herrero, Pablo; García-Sánchez, Yolanda; Jones, Peter G

2009-03-02

The reaction of AgClO(4) with piperidinium 2,7-di-tert-butyl-9H-fluorene-9-carbodithioate (pipH)[S(2)C(t-Bu-Hfy)] (1) (t-Bu-Hfy = 2,7-di-tert-butylfluoren-9-yl) afforded [Ag(n){S(2)C(t-Bu-Hfy)}(n)] (2), which reacted with phosphines to give [Ag{S(2)C(t-Bu-Hfy)}L(2)] [L = PPh(3) (3a); L(2) = bis(diphenylphosphino)ethane (dppe, 3b), 1,1'-bis(diphenylphosphino)ferrocene (dppf, 3c). By reacting complex 2 with AgClO(4) and piperidine in a 1:1:1 molar ratio, the dodecanuclear cluster [Ag(12){S(2)C(t-Bu-fy)}(6)] (4) (t-Bu-fy = 2,7-di-tert-butylfluoren-9-ylidene) was obtained. Compound 4 can also be directly prepared from the reaction of 1 with AgClO(4) and piperidine in a 1:2:1 molar ratio. The reactions of 1 with AgClO(4), phosphines, and piperidine afforded the compounds [Ag(6){S(2)C(t-Bu-fy)}(3)L(5)] [1:2:2:1 molar ratio; L = PPh(3) (5a), P(p-To)(3) (5b)], [Ag(4){S(2)C(t-Bu-fy)}(2)(dppf)(2)] (6) (1:2:1:1 molar ratio), [Ag(n){S(2)C(t-Bu-fy)}(n/2){P(i-Pr)(3)}(n)] (7) (1:2:2:1 molar ratio), or [Ag(8){S(2)C(t-Bu-fy)}(4){P(i-Pr)(3)}(4)] (8) (1:2:1:1 molar ratio). Complexes 5a,b, 6, 7, and 8 can be also obtained by reacting 4 with the corresponding phosphine in the appropriate molar ratio. The crystal structures of 4, 5b, and 8 have been determined by X-ray diffraction studies. The nuclearity of complex 6 was established from its (31)P{(1)H} NMR data, which reveal a very fast dynamic process leading to an average coupling of each of the P atoms of the dppf ligands with four Ag atoms.

Aquatic toxicity of four alkylphenols (3-tert-butylphenol, 2-isopropylphenol, 3-isopropylphenol, and 4-isopropylphenol) and their binary mixtures to microbes, invertebrates, and fish.

PubMed

Choi, Kyungho; Sweet, Leonard I; Meier, Peter G; Kim, Pan-Gyi

2004-02-01

The acute and chronic toxicity of four simple alkylphenols with butyl and propyl substitutions was evaluated with aquatic microbes, invertebrates, and fish. These alkylphenols-3-tert-butylphenol, 2-isopropylphenol, 3-isopropylphenol, and 4-isopropylphenol-have been detected in various environmental media, but their impact on aquatic fauna has seldom been evaluated. Relative susceptibility to each phenolic varied by test species. The marine bacterium Vibrio fischeri was the most susceptible to the alkylphenols, up to 3 orders of magnitude more sensitive than species of higher trophic levels. For 4-isopropylphenol, the 5-min Microtox EC(50) value was 0.01 mg/L, whereas the EC(50) for Ceriodaphnia after a 48-h exposure was 10.1 mg/L. Notable differences in sensitivity to the alkylphenols was also observed with the Microtox assay: 4-isopropylphenol was > 200 times more toxic to V. fischeri than was 2-isopropylphenol (EC(50) = 2.72 mg/L). For V. fischeri, the mixture toxicity of the alkylphenols was additive in nature and was predicted by a concentration addition model. The energy of the lowest unoccupied molecular orbital (ELUMO) explained the observed toxicity of the individual alkylphenols to V. fischeri (r(2) = 0.92, p < 0.05). These results suggest that the mode of action of polar narcotic alkylphenols to V. fischeri is different than that of other test organisms, possibly because of the differences in the cell structure of the prokaryotic V. fischeri. Copyright 2004 Wiley Periodicals, Inc. Environ Toxicol 19: 45-50, 2004.

Low coordinated mononuclear erbium(iii) single-molecule magnets with C3v symmetry: a method for altering single-molecule magnet properties by incorporating hard and soft donors.

PubMed

Zhang, Haitao; Nakanishi, Ryo; Katoh, Keiichi; Breedlove, Brian K; Kitagawa, Yasutaka; Yamashita, Masahiro

2018-01-02

Structures and magnetic characteristics of two three-coordinate erbium(iii) compounds with C 3v geometry, tris(2,6-di-tert-butyl-p-cresolate)erbium, Er(dbpc) 3 (1) and tris(bis(trimethylsilyl)methyl)erbium, Er(btmsm) 3 (2), were determined. Both underwent temperature-dependent slow magnetic relaxation processes in the absence of an external magnetic field. As a result of the differences in the coordination environment, they exhibit different energy barriers and quantum tunneling of magnetization (QTM) constants.

Isolation and Characterization of 4-tert-Butylphenol-Utilizing Sphingobium fuliginis Strains from Phragmites australis Rhizosphere Sediment▿ †

PubMed Central

Toyama, Tadashi; Momotani, Naonori; Ogata, Yuka; Miyamori, Yuji; Inoue, Daisuke; Sei, Kazunari; Mori, Kazuhiro; Kikuchi, Shintaro; Ike, Michihiko

2010-01-01

We isolated three Sphingobium fuliginis strains from Phragmites australis rhizosphere sediment that were capable of utilizing 4-tert-butylphenol as a sole carbon and energy source. These strains are the first 4-tert-butylphenol-utilizing bacteria. The strain designated TIK-1 completely degraded 1.0 mM 4-tert-butylphenol in basal salts medium within 12 h, with concomitant cell growth. We identified 4-tert-butylcatechol and 3,3-dimethyl-2-butanone as internal metabolites by gas chromatography-mass spectrometry. When 3-fluorocatechol was used as an inactivator of meta-cleavage enzymes, strain TIK-1 could not degrade 4-tert-butylcatechol and 3,3-dimethyl-2-butanone was not detected. We concluded that metabolism of 4-tert-butylphenol by strain TIK-1 is initiated by hydroxylation to 4-tert-butylcatechol, followed by a meta-cleavage pathway. Growth experiments with 20 other alkylphenols showed that 4-isopropylphenol, 4-sec-butylphenol, and 4-tert-pentylphenol, which have alkyl side chains of three to five carbon atoms with α-quaternary or α-tertiary carbons, supported cell growth but that 4-n-alkylphenols, 4-tert-octylphenol, technical nonylphenol, 2-alkylphenols, and 3-alkylphenols did not. The rate of growth on 4-tert-butylphenol was much higher than that of growth on the other alkylphenols. Degradation experiments with various alkylphenols showed that strain TIK-1 cells grown on 4-tert-butylphenol could degrade 4-alkylphenols with variously sized and branched side chains (ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, tert-octyl, n-nonyl, and branched nonyl) via a meta-cleavage pathway but not 2- or 3-alkylphenols. Along with the degradation of these alkylphenols, we detected methyl alkyl ketones that retained the structure of the original alkyl side chains. Strain TIK-1 may be useful in the bioremediation of environments polluted by 4-tert-butylphenol and various other 4-alkylphenols. PMID:20802076

CONCENTRATIONS, SOURCES, AND FATE OF THE GASOLINE OXYGENATE METHYL TERT-BUTYL ETHER (MTBE) IN A MULTIPLE-USE LAKE. (R826282)

EPA Science Inventory

Discovery of the fuel additive methyl tert-butyl ether (MTBE) in
drinking water supplies is of concern to public health officials, water
suppliers, and the public. Despite recent policy decisions, few published
studies exist on the concentrations, sources, a...

INTERACTION OF METHYL-TERT BUTYL ETHER AND WATER STRESS ON SEED GERMINATION AND SEEDLING GROWTH IN SOIL MICROCOSMS

EPA Science Inventory

Methyl tert-butyl ether (MTBE) is a widespread contaminant in surface and ground water in the United States. Frequently irrigation is used to water fields to germinate planted seeds and sustain plant growth. A likely possibility exists that water used may have some MTBE. Our s...

The quantitative surface analysis of an antioxidant additive in a lubricant oil matrix by desorption electrospray ionization mass spectrometry

PubMed Central

Da Costa, Caitlyn; Reynolds, James C; Whitmarsh, Samuel; Lynch, Tom; Creaser, Colin S

2013-01-01

RATIONALE Chemical additives are incorporated into commercial lubricant oils to modify the physical and chemical properties of the lubricant. The quantitative analysis of additives in oil-based lubricants deposited on a surface without extraction of the sample from the surface presents a challenge. The potential of desorption electrospray ionization mass spectrometry (DESI-MS) for the quantitative surface analysis of an oil additive in a complex oil lubricant matrix without sample extraction has been evaluated. METHODS The quantitative surface analysis of the antioxidant additive octyl (4-hydroxy-3,5-di-tert-butylphenyl)propionate in an oil lubricant matrix was carried out by DESI-MS in the presence of 2-(pentyloxy)ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate as an internal standard. A quadrupole/time-of-flight mass spectrometer fitted with an in-house modified ion source enabling non-proximal DESI-MS was used for the analyses. RESULTS An eight-point calibration curve ranging from 1 to 80 µg/spot of octyl (4-hydroxy-3,5-di-tert-butylphenyl)propionate in an oil lubricant matrix and in the presence of the internal standard was used to determine the quantitative response of the DESI-MS method. The sensitivity and repeatability of the technique were assessed by conducting replicate analyses at each concentration. The limit of detection was determined to be 11 ng/mm2 additive on spot with relative standard deviations in the range 3–14%. CONCLUSIONS The application of DESI-MS to the direct, quantitative surface analysis of a commercial lubricant additive in a native oil lubricant matrix is demonstrated. © 2013 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons, Ltd. PMID:24097398

Rhenium Complex with Noninnocent Dioxolene Ligand: Combined Experimental and ab Initio Study of [(3,5-di-tert-Bu2C6H2O2)ReCl3(OPPh3)].

PubMed

Abramov, Pavel A; Gritsan, Nina P; Suturina, Elizaveta A; Bogomyakov, Artem S; Sokolov, Maxim N

2015-07-20

Reaction of [ReOCl3(PPh3)2] with 3,5-di-tert-butyl-1,2-benzoquinone (3,5-DTBQ) in hot toluene produces a new complex [(3,5-di-tert-Bu2C6H2O2)Re(OPPh3)Cl3] (1), which was isolated and characterized by elemental analysis, IR, UV-vis spectroscopy, and cyclic voltammetry. In order to clarify the charge state of rhenium and the coordinated dioxolene ligand, X-ray experiments at 150 and 290 K were carried out. The C-O, C-C, and Re-O bond distances at both 150 and 290 K fall between those for semiquinolate (3,5-DTBSQ) and catecholate (3,5-DTBCat) forms; an empirical "metrical oxidation state" of the dioxolene ligand was estimated to be -1.5. High-level ab initio calculations (SOC-CASSCF/NEVPT2) revealed a mixed valence nature of the triplet ground state of complex 1 corresponding to a superposition of the Re(IV)-SQ and Re(V)-cat forms. In agreement with the high-level ab initio and DFT calculations, the temperature dependence of the magnetic susceptibility (5-300 K) is well described in the assumption of the triplet ground state, with the anomalously large zero-field splitting (ZFS) arising from the spin-orbit coupling. According to the ab initio calculations, all absorption bands in the visible region of the electronic absorptions spectrum are assigned to the LMCT bands, with significant contribution of the intraligand transition in the most intense band at 555 nm.

Identification of leachable impurities in an ophthalmic drug product originating from a polymer additive Irganox 1010 using mass spectroscopy.

PubMed

Singh, Gagandeep; Gollapalli, Ramarao; Blinder, Alejandro; Patel, Milan

2018-04-15

Pharmaceutical packaging employs a wide variety of polymers owing to their desirable features, but the compounds that could leach from the polymers into the drug products can pose serious health risks. Therefore, it is extremely important to identify such compounds so that they can be adequately quantified and evaluated for toxicological impact/safety assessments. Not only the polymer components and the additives should be considered as sources for leachable impurities, their reaction/degradation products should also be evaluated. Irganox 1010 is a common commercial antioxidant (polymer additive) used in the manufacturing of polyolefin materials for container closure systems. In our study, we identified two Irganox1010 related leachable impurities in an ophthalmic drug product using rapid and straightforward orthogonal mass spectroscopy (LC-MS and GC-MS) methods The identified impurities were 7,9-Di-tert-butyl-1 oxaspiro[4.5]deca-6,9-diene-2,8-dione and 3-[3,5-bis(tert-butyl)-1-hydroxy-4-oxocyclohexa-2,5-dienyl]propanoic acid which leached into the ophthalmic drug solution during storage. The analytical methods employed could potentially be used to identify the similar class of compounds as is or in drug products. Copyright © 2018 Elsevier B.V. All rights reserved.

SrCo1−xTixO3−δ perovskites as excellent catalysts for fast degradation of water contaminants in neutral and alkaline solutions

PubMed Central

Miao, Jie; Sunarso, Jaka; Su, Chao; Zhou, Wei; Wang, Shaobin; Shao, Zongping

2017-01-01

Perovskite-like oxides SrCo1−xTixO3−δ (SCTx, x = 0.1, 0.2, 0.4, 0.6) were used as heterogeneous catalysts to activate peroxymonosulfate (PMS) for phenol degradation under a wide pH range, exhibiting more rapid phenol oxidation than Co3O4 and TiO2. The SCT0.4/PMS system produced a high activity at increased initial pH, achieving optimized performance at pH ≥ 7 in terms of total organic carbon removal, the minimum Co leaching and good catalytic stability. Kinetic studies showed that the phenol oxidation kinetics on SCT0.4/PMS system followed the pseudo-zero order kinetics and the rate on SCT0.4/PMS system decreased with increasing initial phenol concentration, decreased PMS amount, catalyst loading and solution temperature. Quenching tests using ethanol and tert-butyl alcohol demonstrated sulfate and hydroxyl radicals for phenol oxidation. This investigation suggested promising heterogeneous catalysts for organic oxidation with PMS, showing a breakthrough in the barriers of metal leaching, acidic pH, and low efficiency of heterogeneous catalysis. PMID:28281656

21 CFR 176.200 - Defoaming agents used in coatings.

Code of Federal Regulations, 2014 CFR

2014-04-01

... are provided: List of substances Limitations n-Butyl alcohol tert-Butyl alcohol Butyl stearate Castor... Glyceryl monostearate Hexane Hexylene glycol (2-methyl-2,4-pentanediol) Isobutyl alcohol Isopropyl alcohol...

Release of drinking water contaminants and odor impacts caused by green building cross-linked polyethylene (PEX) plumbing systems.

PubMed

Kelley, Keven M; Stenson, Alexandra C; Dey, Rajarashi; Whelton, Andrew J

2014-12-15

Green buildings are increasingly being plumbed with crosslinked polyethylene (PEX) potable water pipe. Tap water quality was investigated at a six month old plumbing system and chemical and odor quality impacts of six PEX pipe brands were examined. Eleven PEX related contaminants were found in the plumbing system; one regulated (toluene) and several unregulated: Antioxidant degradation products, resin solvents, initiator degradation products, or manufacturing aides. Water chemical and odor quality was monitored for new PEX-a, -b and -c pipes with (2 mg/L free chlorine) and without disinfectant over 30 days. Odor and total organic carbon (TOC) levels decreased for all pipes, but odor remained greater than the USA's Environmental Protection Agency's (USEPA) secondary maximum contaminant level. Odors were not attributed to known odorants ethyl-tert-butyl ether (ETBE) or methyl-tert-butyl ether (MTBE). Free chlorine caused odor levels for PEX-a1 pipe to increase from 26 to 75 threshold odor number (TON) on day 3 and affected the rate at which TOC changed for each brand over 30 days. As TOC decreased, the ultraviolet absorbance at 254 nm increased. Pipes consumed as much as 0.5 mg/L as Cl2 during each 3 day stagnation period. Sixteen organic chemicals were identified, including toluene, pyridine, methylene trichloroacetate and 2,4-di-tert-butylphenol. Some were also detected during the plumbing system field investigation. Six brands of PEX pipes sold in the USA and a PEX-a green building plumbing system impacted chemical and drinking water odor quality. Copyright © 2014 Elsevier Ltd. All rights reserved.

Development and performance of a 129-GHz dynamic nuclear polarizer in an ultra-wide bore superconducting magnet.

PubMed

Lumata, Lloyd L; Martin, Richard; Jindal, Ashish K; Kovacs, Zoltan; Conradi, Mark S; Merritt, Matthew E

2015-04-01

We sought to build a dynamic nuclear polarization system for operation at 4.6 T (129 GHz) and evaluate its efficiency in terms of (13)C polarization levels using free radicals that span a range of ESR linewidths. A liquid helium cryostat was placed in a 4.6 T superconducting magnet with a 150-mm warm bore diameter. A 129-GHz microwave source was used to irradiate (13)C enriched samples. Temperatures close to 1 K were achieved using a vacuum pump with a 453-m(3)/h roots blower. A hyperpolarized (13)C nuclear magnetic resonance (NMR) signal was detected using a saddle coil and a Varian VNMRS console operating at 49.208 MHz. Samples doped with free radicals BDPA (1,3-bisdiphenylene-2-phenylallyl), trityl OX063 (tris{8-carboxyl-2,2,6,6-benzo(1,2-d:4,5-d)-bis(1,3)dithiole-4-yl}methyl sodium salt), galvinoxyl ((2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy), 2,2-diphenylpicrylhydrazyl (DPPH) and 4-oxo-TEMPO (4-Oxo-2,2,6,6-tetramethyl-1-piperidinyloxy) were assayed. Microwave dynamic nuclear polarization (DNP) spectra and solid-state (13)C polarization levels for these samples were determined. (13)C polarization levels close to 50 % were achieved for [1-(13)C]pyruvic acid at 1.15 K using the narrow electron spin resonance (ESR) linewidth free radicals trityl OX063 and BDPA, while 10-20 % (13)C polarizations were achieved using galvinoxyl, DPPH and 4-oxo-TEMPO. At this field strength free radicals with smaller ESR linewidths are still superior for DNP of (13)C as opposed to those with linewidths that exceed that of the (1)H Larmor frequency.

A new piperazine derivative: 1-(4-(3,5-di-tert-butyl-4-hydroxybenzyl) piperazin-1-yl)-2-methoxyethan-1-one with antioxidant and central activity.

PubMed

Brito, Adriane F; Braga, Patrícia C C S; Moreira, Lorrane K S; Silva, Dayane M; Silva, Daiany P B; Sanz, Germán; Vaz, Boniek G; de Carvalho, Flávio S; Lião, Luciano M; Silva, Rafaela R; Noël, François; Neri, Hiasmin F S; Ghedini, Paulo C; de Carvalho, Murilo F; de S Gil, Eric; Costa, Elson A; Menegatti, Ricardo

2018-03-01

In the scope of a research program aimed at developing new drugs for the treatment of central nervous system diseases, we describe herein the synthesis and pharmacological evaluation of 1-(4-(3,5-di-tert-butyl-4-hydroxybenzyl) piperazin-1-yl)-2-methoxyethan-1-one (LQFM180). This compound showed antioxidant activity in two models, electroanalytical assays, and DPPH activity. Moreover, in behavioral tests as the open field test LQFM180 (9.4, 18.8, and 37.6 mg/kg, per oral (p.o.)), we detected anxiolytic-like activity. In the sodium pentobarbital-induced sleep test, LQFM180, in all doses, decreased the latency to sleep and increased sleep duration, indicating central depressant activity; moreover, in the chimney test, LQFM180 did not alter motor activity. LQFM180 (18.8 mg/kg, p.o.) increased the time and number of entries on open arms in the elevated plus maze test, suggesting anxiolytic-like activity, which was reversed by NAN-190 and p-chlorophenylalanine, indicating a role of the serotonergic pathway on this effect. In the forced swimming test, LFQM180 (18.8 mg/kg, p.o.) decreased immobility time, suggesting antidepressant-like activity, which was reversed by monoaminergic antagonists, indicating a role for the serotonergic, noradrenergic, and dopaminergic pathways. Competition binding assays showed that LQFM180 was able to bind to the α 1B , 5-HT 1A , and D 2 receptors, however, within the low micromolar range. We conclude that LQFM180 should be considered as a scaffold for drug candidate development.

In vitro and in vivo effect of 2,6-Di-tert-butyl-4-methylphenol as an antibiofilm agent against quorum sensing mediated biofilm formation of Vibrio spp.

PubMed

Santhakumari, Sivasubramanian; Jayakumar, Rengarajan; Logalakshmi, Ravichandran; Prabhu, Narayanan Marimuthu; Abdul Nazar, Abdul Kuthus; Karutha Pandian, Shunmugiah; Veera Ravi, Arumugam

2018-05-25

This study unveils the in vitro and in vivo antibiofilm potential of 2,6-Di-tert-butyl-4-methylphenol (DTBMP) from Chroococcus turgidus against Vibrio spp. In the preliminary study, cell free culture supernatant (CFCS) of C. turgidus inhibited the violacein production in biomarker strain Chromobacterium violaceum and its mutant strain CV026 in a dose dependent manner. The effective biofilm inhibitory concentration (BIC) of pure compound DTBMP from C. turgidus was identified as 250 μg/ml concentration in tested Vibrio species. Furthermore, DTBMP proved to effectively inhibit the bioluminescence production in V. harveyi and other biofilm related virulence traits such as exopolysaccharides (EPS) production, hydrophobicity index, swimming and swarming motility at its BIC concentration in three major pathogenic vibrios: V. harveyi, V. parahaemolyticus and V. vulnificus. The antibiofilm potential of DTBMP was validated through light, confocal laser scanning and scanning electron microscopic analyses. In addition, the non-bactericidal effect of DTBMP was determined through growth curve and 2,3-bis (2-methyloxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide (XTT) assay. Real-time PCR studies revealed the down-regulation of master quorum sensing (QS) regulator genes of V. harveyi such as luxR, luxS, luxP, luxQ and luxO on treatment with DTBMP. In vivo results confirmed that DTBMP augmented the survival rate of Litopenaeus vannamei larvae up to 75, 88 and 66% upon infection with V. harveyi, V. parahaemolyticus and V. vulnificus, respectively. The results of this study ascertain the promising effects of DTBMP as an antibiofilm agent, which could be positively explored to treat biofilm-associated vibrios infections in aquaculture. Copyright © 2018 Elsevier B.V. All rights reserved.

40 CFR 464.21 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72... 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72...-ethylhexyl) phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl...

40 CFR 464.21 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72... 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72...-ethylhexyl) phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl...

In vitro study comparing the ability of mono-octanoin and mono-octanoin plus methyl tert-butyl ether to dissolve biliary stones.

PubMed

Tritapepe, R; Cesana, B

1996-01-01

This in vitro study compared the gallstone dissolution rates of mono-octanoin, mono-octanoin plus 10% distilled water, and mono-octanoin plus methyl tert-butyl ether 2:1. Sixteen stones were treated with each solvent at a slow perfusion rate of 3-4 ml/h and a rapid perfusion rate of 2.5 ml/30 min with 20-sec instillation/aspiration cycles, both with and without bile. The stones were weighed before, and 3, 6, 12 and 24 hrs after the start of treatment: the solvent was changed every 30 min. After 24 hrs of instillation/aspiration without bile, the mono-octanoin/methyl tert-butyl ether mixture reduced the weight of the stones by 93%, mono-octanoin plus water by 63%, and mono-octanoin alone by 52%; with bile, the figures were, respectively, 86%, 42% and 40%. The mono-octanoin/methyl tert-butyl ether mixture thus took approximately half the time needed by the other two preparations to dissolve the stones to the same extent, a finding which may be relevant for the clinical dissolution of bile duct stones.

Enantioselective syntheses of carbanucleosides from the Pauson-Khand adduct of trimethylsilylacetylene and norbornadiene.

PubMed

Vázquez-Romero, Ana; Rodríguez, Julia; Lledó, Agustí; Verdaguer, Xavier; Riera, Antoni

2008-10-16

A new enantioselective approach to carbanucleosides from Pauson-Khand (PK) adduct 1 is disclosed. The chiral cyclopentenone 1 is readily accessible in enantiomerically pure form via PK reaction of trimethylsilylacetylene and norbornadiene using N-benzyl-N-diphenylphosphino-tert-butyl-sulfinamide as a chiral P,S ligand. (-)-Carbavir and (-)-Abacavir were enantioselectively synthesized starting from (-)-1. The key steps of the sequence are a photochemical conjugate addition of a hydroxymethyl radical, a retro-Diels-Alder reaction, and a palladium catalyzed allylic substitution to introduce the nucleobase.

Hydrolysis of the quinone methide of butylated hydroxytoluene in aqueous solutions.

PubMed

Willcockson, Maren Gulsrud; Toteva, Maria M; Stella, Valentino J

2013-10-01

Butylated hydroxytoluene or BHT is an antioxidant commonly used in pharmaceutical formulations. BHT upon oxidation forms a quinone methide (QM). QM is a highly reactive electrophilic species that can undergo nucleophilic addition. Here, the kinetic reactivity of QM with water at various apparent pH values in a 50% (v/v) water-acetonitrile solution at constant ionic strength of I = 0.5 (NaCl)4 , was studied. The hydrolysis of QM in the presence of added acid, base, sodium chloride, and phosphate buffer resulted in the formation of only one product--the corresponding 3,5-di-tert-butyl-4-hydroxybenzyl alcohol (BA). The rate of BA formation was catalyzed by the addition of acid and base, but not chloride and phosphate species. Nucleophilic excipients, used in the pharmaceutical formulation, or nucleophilic groups on active pharmaceutical ingredient molecule may form adducts with QM, the immediate oxidative product of BHT degradation, thus having implications for drug product impurity profiles. Because of these considerations, BHT should be used with caution in formulations containing drugs or excipients capable of acting as nucleophiles. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Sequestering ability of butylated hydroxytoluene, propyl gallate, resveratrol, and vitamins C and E against ABTS, DPPH, and hydroxyl free radicals in chemical and biological systems.

PubMed

Soares, Daniele G; Andreazza, Ana C; Salvador, Mirian

2003-02-12

The antioxidant capacity of butylated hydroxytoluene (BHT; 2,6-di-tert-butyl-p-cresol), propyl gallate (3,4,5-trihydroxybenzoic acid n-propyl ester), resveratrol (trans-3,4',5-trihydroxystilbene), and vitamins C (l-ascorbic acid) and E [(+)-alpha-tocopherol] was studied in chemical and biological systems. The chemical assays evaluated the capacity of these antioxidants to sequester 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS.) and 1,1 diphenyl-2-picrylhydrazyl (DPPH.). A new colorimetric method to determine hydroxyl radical scavenging is also described. The biological tests use the eucaryotic cells of Saccharomyces cerevisiae treated with the antioxidants in the presence of the stressing agents apomorphine, hydrogen peroxide, and paraquat dichloride (methylviologen; 1,1'-dimethyl-4,4'-bipyridinium dichloride). The results in chemical systems showed that all of the antioxidants were able to significantly inhibit the oxidation of beta-carotene by hydroxyl free radicals. The assays in yeast showed that the antioxidant activity of the tested compounds depended on the stressing agent used and the mechanism of action of the antioxidant.

Thin PDMS Films Using Long Spin Times or Tert-Butyl Alcohol as a Solvent

PubMed Central

Koschwanez, John H.; Carlson, Robert H.; Meldrum, Deirdre R.

2009-01-01

Thin polydimethylsiloxane (PDMS) films are frequently used in “lab on a chip” devices as flexible membranes. The common solvent used to dilute the PDMS for thin films is hexane, but hexane can swell the underlying PDMS substrate. A better solvent would be one that dissolves uncured PDMS but doesn't swell the underlying substrate. Here, we present protocols and spin curves for two alternatives to hexane dilution: longer spin times and dilution in tert-butyl alcohol. The thickness of the PDMS membranes under different spin speeds, spin times, and PDMS concentrations was measured using an optical profilometer. The use of tert-butyl alcohol to spin thin PDMS films does not swell the underlying PDMS substrate, and we have used these films to construct multilayer PDMS devices. PMID:19238212

Soluble, High Molecular Weight Polysilsesquioxanes with Carboxylate Functionalities

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

RAHIMIAN,KAMYAR; LOY,DOUGLAS A.; WHEELER,DAVID R.

2000-07-14

Trialkoxysilyl-containing monomers of the type (RO){sub 3}Si(CH{sub 2}){sub 3}C(O)OtBu (R = Me, Et) were prepared by hydrosilation of the corresponding vinylic tert-butyl esters CH{sub 3}CHCH{sub 2}C(O)OtBu. Acid- or base-catalyzed polymerization of the monomers leads to very high molecular weight polymers with relatively narrow polydispersities. The polymerization results in complete condensation of the alkoxy groups while the tert-butyl ester functionality remains fully intact. Partial or full deprotection of the tert-butyl group can easily be achieved to yield the corresponding carboxylic acid polymers. The ester and carboxylic acid functionalities of these new materials allow for their potential use in a variety ofmore » applications such as scavenging of heavy metals.« less

IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) ...

EPA Pesticide Factsheets

On April 29, 2016, the Toxicological Review of tert-Butyl Alcohol (tert-Butanol) (Public Comment Draft) was released for public comment. The draft Toxicological Review and charge were reviewed internally by EPA and by other federal agencies and the Executive Office of the President during Step 3 (Interagency Science Consultation) before public release. As part of the IRIS process, all written interagency comments on IRIS assessments will be made publicly available. Accordingly, interagency comments with EPA's response and the interagency science consultation drafts of the IRIS Toxicological Review of tert-Butanol and charge to external peer reviewers are posted on this site. EPA is undertaking a new health assessment for t-butyl alcohol (tert-butanol) for the Integrated Risk Information System (IRIS). The outcome of this project will be a Toxicological Review and IRIS and IRIS Summary of TBA that will be entered on the IRIS database. IRIS is an EPA database containing Agency scientific positions on potential adverse human health effects that may result from chronic (or lifetime) exposure to chemicals in the environment. IRIS contains chemical-specific summaries of qualitative and quantitative health information to evaluate potential public health risks associated with environmental contaminants. The IRIS database is relied on for the development of risk assessments, site-specific environmental decisions, and rule making.

tert-Butyl 6-amino-5-cyano-2-(2-meth­oxy­eth­yl)nicotinate

PubMed Central

Chen, Yi-Ning; Zhao, Xing-Dong; Deng, Jie; Li, Qin-Geng

2012-01-01

The title compound, C14H19N3O3, was synthesized by the reaction of 3-meth­oxy­propionitrile, tert-butyl bromo­acetate and eth­oxy­methyl­enemalononitrile. In the crystal, N—H⋯O hydrogen bonds link the mol­ecules into chains propagating along the b axis. PMID:22737103

Enantioselective Synthesis of Chiral α-Azido and α-Aryloxy Quaternary Stereogenic Centers via the Phase-Transfer-Catalyzed α-Alkylation of α-Bromomalonates, Followed by SN2 Substitution.

PubMed

Kim, Doyoung; Ha, Min Woo; Hong, Suckchang; Park, Cheonhyoung; Kim, Byungsoo; Yang, Jewon; Park, Hyeung-Geun

2017-05-05

A new efficient synthetic method for chiral α-azido-α-alkylmalonates and α-aryloxy-α-alkylmalonates was developed. The enantioselective α-alkylation of diphenylmethyl tert-butyl α-bromomalonate under phase-transfer catalytic conditions [(S,S)-3,4,5-trifluorophenyl-NAS bromide, 50% KOH, toluene, and -40 °C) provided the corresponding α-bromo-α-alkylmalonates in high chemical yields (≤98%) and high optical yields (≤99% ee). The resulting α-alkylated products were converted to α-azido-α-alkylmalonates (≤96%, ≤97% ee) and α-aryloxy-α-alkylmalonates (≤79%, ≤93% ee) by S N 2 substitution with sodium azide and aryloxides, respectively.

Vanadium(V) Complexes with Substituted 1,5-bis(2-hydroxybenzaldehyde)carbohydrazones and Their Use As Catalyst Precursors in Oxidation of Cyclohexane.

PubMed

Dragancea, Diana; Talmaci, Natalia; Shova, Sergiu; Novitchi, Ghenadie; Darvasiová, Denisa; Rapta, Peter; Breza, Martin; Galanski, Markus; Kožı́šek, Jozef; Martins, Nuno M R; Martins, Luísa M D R S; Pombeiro, Armando J L; Arion, Vladimir B

2016-09-19

Six dinuclear vanadium(V) complexes have been synthesized: NH4[(VO2)2((H)LH)] (NH4[1]), NH4[(VO2)2((t-Bu)LH)] (NH4[2]), NH4[(VO2)2((Cl)LH)] (NH4[3]), [(VO2)(VO)((H)LH)(CH3O)] (4), [(VO2)(VO)((t-Bu)LH)(C2H5O)] (5), and [(VO2)(VO)((Cl)LH)(CH3O)(CH3OH/H2O)] (6) (where (H)LH4 = 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone, (t-Bu)LH4 = 1,5-bis(3,5-di-tert-butyl-2-hydroxybenzaldehyde)carbohydrazone, and (Cl)LH4 = 1,5-bis(3,5-dichloro-2-hydroxybenzaldehyde)carbohydrazone). The structures of NH4[1] and 4-6 have been determined by X-ray diffraction (XRD) analysis. In all complexes, the triply deprotonated ligand accommodates two V ions, using two different binding sites ONN and ONO separated by a diazine unit -N-N-. In two pockets of NH4[1], two identical VO2(+) entities are present, whereas, in those of 4-6, two different VO2(+) and VO(3+) are bound. The highest oxidation state of V ions was corroborated by X-ray data, indicating the presence of alkoxido ligand bound to VO(3+) in 4-6, charge density measurements on 4, magnetic susceptibility, NMR spectroscopy, spectroelectrochemistry, and density functional theory (DFT) calculations. All four complexes characterized by XRD form dimeric associates in the solid state, which, however, do not remain intact in solution. Compounds NH4[1], NH4[2], and 4-6 were applied as alternative selective homogeneous catalysts for the industrially significant oxidation of cyclohexane to cyclohexanol and cyclohexanone. The peroxidative (with tert-butyl hydroperoxide, TBHP) oxidation of cyclohexane was performed under solvent-free and additive-free conditions and under low-power microwave (MW) irradiation. Cyclohexanol and cyclohexanone were the only products obtained (high selectivity), after 1.5 h of MW irradiation. Theoretical calculations suggest a key mechanistic role played by the carbohydrazone ligand, which can undergo reduction, instead of the metal itself, to form an active reduced form of the catalyst.

Insights into the Hydrogen-Atom Transfer of the Blue Aroxyl.

PubMed

Bächle, Josua; Marković, Marijana; Kelterer, Anne-Marie; Grampp, Günter

2017-10-19

An experimental and theoretical study on hydrogen-atom transfer dynamics in the hydrogen-bonded substituted phenol/phenoxyl complex of the blue aroxyl (2,4,6-tri-tert-butylphenoxyl) is presented. The experimental exchange dynamics is determined in different organic solvents from the temperature-dependent alternating line-width effect in the continuous-wave ESR spectrum. From bent Arrhenius plots, effective tunnelling contributions with parallel heavy-atom motion are concluded. To clarify the transfer mechanism, reaction paths for different conformers of the substituted phenol/phenoxyl complex are modelled theoretically. Various DFT and post-Hartree-Fock methods including multireference methods are applied. From the comparison of experimental and theoretical data it is concluded that the system favours concerted hydrogen-atom transfer along a parabolic reaction path caused by heavy-atom motion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

N,N′-Di-tert-butyl-N′′-(2,6-difluoro­benzo­yl)phospho­ric triamide

PubMed Central

Pourayoubi, Mehrdad; Tarahhomi, Atekeh; Rheingold, Arnold L.; Golen, James A.

2010-01-01

In the title compound, C15H24F2N3O2P, the phosphoryl and carbonyl groups adopt anti positions relative to each other. The P atom is in a tetra­hedral coordination environment and the environment of each N atom is essentially planar. In the crystal, adjacent mol­ecules are linked via N—H⋯O=P and N—H⋯O=C hydrogen bonds into an extended chain parallel to the a axis. The crystal studied was a non-merohedral twin with a minor twin component of 36.4 (1)%. PMID:21589456

Photooxidation of 3-substituted pyrroles:  a postcolumn reaction detection system for singlet molecular oxygen in HPLC.

PubMed

Denham, K; Milofsky, R E

1998-10-01

A postcolumn photochemical reaction detection scheme, based on the reaction of 3-substituted pyrroles with singlet molecular oxygen ((1)O(2)), has been developed. The method is selective and sensitive for the determination of a class of organic compounds called (1)O(2)-sensitizers and is readily coupled to HPLC. Following separation by HPLC, analytes ((1)O(2)-sensitizers) are excited by a Hg pen-ray lamp. Analytes that are efficient (1)O(2)-sensitizers promote ground-state O(2) ((3)Σ(g)(-)) to an excited state ((1)Σ(g)(+) or (1)Δ(g)), which reacts rapidly with tert-butyl-3,4,5-trimethylpyrrolecarboxylate (BTMPC) or N-benzyl-3-methoxypyrrole-2-tert-carboxylate (BMPC), which is added to the mobile phase. Detection is based on the loss of pyrrole (BTMPC or BMPC). The reaction is catalytic in nature since one analyte molecule may absorb light many times, producing large amounts of (1)O(2). Detection limits for several (1)O(2)-sensitizers were improved by 1-2 orders of magnitude over optimized UV-absorbance detection. This paper discusses the optimization of the reaction conditions for this photochemical reaction detection scheme and its application to the detection of PCBs, nitrogen heterocycles, nitro and chloro aromatics, and other substituted aromatic compounds.

5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetra­methoxy­calix[4]arene dichloro­methane hemisolvate

PubMed Central

Fischer, Conrad; Gruber, Tobias; Seichter, Wilhelm; Schindler, Diana; Weber, Edwin

2008-01-01

In the title compound, C48H64O4·0.5CH2Cl2, both crystallographically independent calixarene mol­ecules display a partial cone conformation. Their crystal packing is stabilized by C—H⋯π contacts involving the meth­oxy groups. The solvent mol­ecule is located inter­stitially between two calixarene units with C—H⋯Cl contacts to meth­oxy and tert-butyl groups. One tert-butyl residue of each calixarene mol­ecule is disordered over two positions (occupancies 0.60/0.40 and 0.63/0.37), resulting in bond distances that deviate from ideal values. The tetra­mer calixarene mol­ecules present models with approximate non-crystallographic Cs symmetry. PMID:21202066

A recyclable ionic liquid-oxomolybdenum(vi) catalytic system for the oxidative desulfurization of model and real diesel fuel.

PubMed

Julião, Diana; Gomes, Ana C; Pillinger, Martyn; Valença, Rita; Ribeiro, Jorge C; Gonçalves, Isabel S; Balula, Salete S

2016-10-14

The oxidative desulfurization of model and real diesel has been studied using the complex [MoO2Cl2(4,4'-di-tert-butyl-2,2'-bipyridine)] as (pre)catalyst, aq. H2O2 as oxidant, and an ionic liquid as extraction solvent. Under moderate conditions (50 °C) and short reaction times (<3 h), dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene could be completely removed from the model diesel. The (pre)catalyst 1 was transformed in situ to the active catalyst [MoO(O2)2(di-tBu-bipy)]. By sequentially performing extractive desulfurization and ECODS steps, 76% sulfur removal was achieved for a real diesel (Sinitial = 2300 ppm). For both the model and real diesels, the catalyst/IL phase could be easily recycled and reused with no loss of desulfurization efficiency.

High-brightness blue organic light emitting diodes with different types of guest-host systems

NASA Astrophysics Data System (ADS)

Wang, Xiao; Zhang, Jing-shuang; Peng, Cui-yun; Guo, Kun-ping; Wei, Bin; Zhang, Hao

2016-03-01

We demonstrate high-brightness blue organic light emitting diodes (OLEDs) using two types of guest-host systems. A series of blue OLEDs were fabricated using three organic emitters of dibenz anthracene (perylene), di(4-fluorophenyl) amino-di (styryl) biphenyl (DSB) and 4,4'-bis[2-(9-ethyl-3-carbazolyl)vinyl]biphenyl (BCzVBi) doped into two hosting materials of 4,4'-bis(9-carbazolyl) biphenyl (CBP) and 2-(4-biphenylyl)-5(4-tert-butyl-phenyl)-1,3,4-oxadiazole (PBD) as blue emitting layers, respectively. We achieve three kinds of devices with colors of deep-blue, pure-blue and sky-blue with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.16, 0.10), (0.15, 0.15) and (0.17, 0.24), respectively, by employing PBD as host material. In addition, we present a microcavity device using the PBD guest-host system and achieve high-purity blue devices with narrowed spectrum.

Unexpected complexes from meta-phenylene bis(tert-butyl nitroxides) and gadolinium(III) 1,1,1,5,5,5-hexafluoropentane-2,4-dionate

NASA Astrophysics Data System (ADS)

Sekine, Hiroyasu; Ishida, Takayuki

2018-01-01

Coordination reaction of the stable ground triplet biradical biphenyl-3,5-diyl bis(tert-butyl nitroxide) and [Gd(hfac)3(H2O)2] unexpectedly gave complexes containing a dimerized diamagnetic ligand via a [3+3] cycloaddition of the benzene rings (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate). To avoid such dimerization, we introduced a bulkier substituent into the ligand; namely, a new ground triplet biradical 5-mesityl-1,3-phenylene bis(tert-butyl nitroxide) was applied to this complexation scheme. However, an unexpected complex was again obtained in a different way, and the magnetic study revealed that the novel ligand involved was diamagnetic. The crystallographic analysis of the product clarified isomerization from the paramagnetic ligand to a diamagnetic N-tert-butylaminoquinone imine N-oxide ligand as a result of disproportionation from two open-shell nitroxide groups to closed-shell groups, an amine and a nitrone. The present paper reports the first structural evidence for a diamagnetic isomer of m-phenylene-bridged bisnitroxde compounds.

Bromine catalyzed conversion of S-tert-butyl groups into versatile and, for self-assembly processes accessible, acetyl-protected thiols.

PubMed

Blaszczyk, Alfred; Elbing, Mark; Mayor, Marcel

2004-10-07

The facile and efficient conversion of a tert-butyl protecting group to an acetyl protecting group for thiols by catalytic amounts of bromine in acetyl chloride and the presence of acetic acid has been developed. The fairly mild reaction conditions are of particular interest for new protecting group strategies for sulfur functionalised target structures. Copyright 2004 The Royal Society of Chemistry

Vibrational spectra and ab initio analysis of tert-butyl, trimethylsilyl, and trimethylgermyl derivatives of 3,3-dimethylcyclopropene . VI: Application of observed trends to stannyl derivatives

NASA Astrophysics Data System (ADS)

Panchenko, Yu. N.; De Maré, G. R.; Abramenkov, A. V.; Baird, M. S.; Tverezovsky, V. V.; Nizovtsev, A. V.; Bolesov, I. G.

2004-09-01

The effects of substitution of X=C by Si or Ge in X(CH 3) 3 moieties attached to the formal double bond of 3,3-dimethylcyclopropene are examined. Regularities in observed trends of vibrational frequencies implicating the moieties containing the X atom, as the X atomic mass is increased, are extrapolated to X=Sn. The results of this extrapolation made it possible to assign the known experimental vibrational frequencies of 3,3-dimethyl-1-(trimethylstannyl)cyclopropene and 3,3-dimethyl-1,2-bis(trimethylstannyl)cyclopropene.

Volatile organic components migrating from plastic pipes (HDPE, PEX and PVC) into drinking water.

PubMed

Skjevrak, Ingun; Due, Anne; Gjerstad, Karl Olav; Herikstad, Hallgeir

2003-04-01

High-density polyethylene pipes (HDPE), crossbonded polyethylene pipes (PEX) and polyvinyl chloride (PVC) pipes for drinking water were tested with respect to migration of volatile organic components (VOC) to water. The odour of water in contact with plastic pipes was assessed according to the quantitative threshold odour number (TON) concept. A major migrating component from HDPE pipes was 2,4-di-tert-butyl-phenol (2,4-DTBP) which is a known degradation product from antioxidants such as Irgafos 168(R). In addition, a range of esters, aldehydes, ketones, aromatic hydrocarbons and terpenoids were identified as migration products from HDPE pipes. Water in contact with HDPE pipes was assessed with respect to TON, and values > or =4 were determined for five out of seven brands of HDPE pipes. The total amount of VOC released to water during three successive test periods were fairly constant for the HDPE pipes. Corresponding migration tests carried out for PEX pipes showed that VOC migrated in significant amounts into the test water, and TON >/=5 of the test water were observed in all tests. Several of the migrated VOC were not identified. Oxygenates predominated the identified VOC in the test water from PEX pipes. Migration tests of PVC pipes revealed few volatile migrants in the test samples and no significant odour of the test water.

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2013 CFR

2013-10-01

...-Amyl methyl ether (Methyl tert-pentyl ether) C Amyl methyl ketone, see Methyl amyl ketone D Animal and... heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone n-Butyl propionate C Butyl stearate III... alcohol (all isomers) C Diisobutylene B Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate...

Effects of Ammonium Dinitramide in Human Liver Slices: An EPR/Spin Trapping Study.

DTIC Science & Technology

1995-09-01

environmentally safe than AP. EPR/spin trapping studies with the spin trap N-tert-butyl-a-phenyl nitrone (PBN lOmM) for 5 min in the presence of ADN yielded...N-tert-butyl-a-phenyl nitrone PBN 17. SECURITY CLASSIFICATION OF REPORT UNCLASSIFIED 18. SECURITY CLASSIFICATION OF THIS PAGE UNCLASSIFIED... nitrone s second SCN- thiocyanate SD standard deviation Vll INTRODUCTION This is a study of the reactions of free radicals formed when ammonium

The First Seven-Coordinated Triiodo Complex of Rhenium(III)

NASA Astrophysics Data System (ADS)

Schoultz, X.; Gerber, T. I. A.; Betz, R.; Hosten, E. C.

2017-12-01

The reaction of cis-[ReO2I(P Ph 3)2] with tert-butyl isocyanide in benzene led to the isolation of the complex [ReI3(CN- t-Bu)3(P Ph 3)] ( 1). The complex is unusual since it contains bulky ligands with large cone angles, i.e. three iodides, three isocyanides with tert-butyl groups and a triphenylphosphine as ligands in a seven-coordinate geometry around the rhenium(III) metal ion.

Synthesis and solution self-assembly of side-chain cobaltocenium-containing block copolymers.

PubMed

Ren, Lixia; Hardy, Christopher G; Tang, Chuanbing

2010-07-07

The synthesis of side-chain cobaltocenium-containing block copolymers and their self-assembly in solution was studied. Highly pure monocarboxycobaltocenium was prepared and subsequently attached to side chains of poly(tert-butyl acrylate)-block-poly(2-hydroxyethyl acrylate), yielding poly(tert-butyl acrylate)-block-poly(2-acryloyloxyethyl cobaltoceniumcarboxylate). The cobaltocenium block copolymers exhibited vesicle morphology in the mixture of acetone and water, while micelles of nanotubes were formed in the mixture of acetone and chloroform.

High temperature concrete composites containing organosiloxane crosslinked copolymers

DOEpatents

Zeldin, A.; Carciello, N.; Kukacka, L.; Fontana, J.

High temperature polymer concrete composites comprising about 10 to 30% by weight of a liquid monomer mixture is described. It consists essentially of an organosiloxane polymer crosslinked with an olefinically unsaturated monomer selected from the group consisting of styrene, methyl methacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, n-phenylmalimide, divinyl benzene and mixtures thereof. About 70 to 90% by weight of an inert inorganic filler system containing silica sand and portland cement, Fe/sub 2/O/sub 3/, carbon black or mixtures thereof. Optionally a free radical initiator such as di-tert-butyl peroxide, azobisisobyutyronitrile, benzoyl peroxide, lauryl peroxide and other organic peroxides are used to initiate crosspolymerization of the monomer mixture in the presence of the inorganic filler.

Evaluation of some antioxidants in radiation vulcanized ethylene-propylene diene (EPDM) rubber

NASA Astrophysics Data System (ADS)

Abdel-Aziz, M. M.; Basfar, A. A.

2001-12-01

Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) have been used to study the oxidation of γ-ray vulcanized ethylene-propylene diene rubber (EPDM) stabilized with various types of antioxidants. The antioxidants used were pentaerythrityl tetrakis(3,5-di-tert-butyl(-4-hydroxyphenyl))propionate (Irganox 1010), Irganox 1035, Irganox 1520D, as primary antioxidants; Irganox B561 and Irganox B900, as synergistic blends; hindered amine light stabilizer (HALS), i.e. Tinuvin 622 LD; N-isopropyl- N-phenyl- p-phenylene diamine (IPPD) and trimethyl quinoline (TMQ) and their mixtures. The measurements were carried out under atmospheric conditions. The effects of antioxidant type and its selected concentration were determined and mechanism of reaction proposed.

Chemical composition and antioxidant activities of the essential oil from Nandina domestica fruits.

PubMed

Bi, Shu-Feng; Zhu, Guang-Qi; Wu, Jie; Li, Zhong-Kang; Lv, Yong-Zhan; Fang, Ling

2016-01-01

The chemical composition and antioxidant activities of the essential oil from Nandina domestica fruits were studied for the first time. Twenty-two compounds, representing 82.79% of the oil, were identified from the oil. The major compounds were 3-hexen-1-ol (12.9%), linalool (12.3%), 2-methoxy-4-vinylphenol (9.9%), oleic acid (8.0%), furfural (5.8%) and 2,6-di-tert-butyl-4-methylphenol (5.7%). The antioxidant activities of the oil were evaluated using reducing power, metal chelating ability and scavenging capacity against 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2'-azinobis-3-ethylbenzthiazoline-6-sulfonate (ABTS) and superoxide anion free radical. The oil exhibited significant antioxidant activities.

Analogues of methotrexate and aminopterin with gamma-methylene and gamma-cyano substitution of the glutamate side chain: synthesis and in vitro biological activity.

PubMed

Rosowsky, A; Bader, H; Freisheim, J H

1991-01-01

Analogues of methotrexate (MTX) and aminopterin (AMT) modified at the gamma-position of the glutamate side chain were synthesized and evaluated as dihydrofolate reductase (DHFR) inhibitors and tumor cell growth inhibitors. Condesations of 4-amino-4-deoxy-N10-methylpteroic acid (mAPA) with dimethyl DL-4-methyleneglutamate in the presence of diethyl phosphorocyanidate (DEPC) followed by alkaline hydrolysis yielded N-(4-amino-4-deoxy-N10-methylpteroyl)-DL-4-methyleneglutamic acid (gamma-methyleneMTX). Condensation of 4-amino-4-deoxy-N10-formylpteroic acid (fAPA) with dimethyl-DL-4-methyleneglutamate by the mixed carboxylic-carbonic anhydride method yielded N-4-amino-4-deoxypteroyl)-DL-4-methyleneglutamic acid (gamma-methyleneAMT). Also prepared via DEPC coupling was a mixture of the four possible diastereomers of N-(4-amino-4-deoxy-N10-methylpteroyl)-4-cyanoglutamic acid (gamma-cyanoMTX). The requisite intermediate gamma-tert-butyl alpha-methyl 4-cyanoglutamate, as a DL-threo/DL-erythro mixture, was prepared from methyl N alpha-Boc-O-tosyl-L-serinate by reaction with sodium tert-butyl cyanoacetate followed by mild trifluoroacetic treatment to selectively remove the Boc group. The gamma-methylene derivatives of MTX and AMT are attractive because of their potential to act as Michael acceptors within the DHFR active site. gamma-CyanoMTX may be viewed as a congener of the nonpolyglutamated MTX analogue gamma-fluoroMTX. In vitro bioassay data for the gamma-methylene and gamma-cyano compounds support the idea that the active site of DHFR, already known for its ability to tolerate modification of the gamma-carboxyl group of MTX and AMT, can likewise accommodate substitution on the gamma-carbon itself.

Hydrolysis of tert-butyl formate: Kinetics, products, and implications for the environmental impact of methyl tert-butyl ether

USGS Publications Warehouse

Church, Clinton D.; Pankow, James F.; Tratnyek, Paul G.

1999-01-01

Asessing the environmental fate of methyl tert-butyl ether (MTBE) has become a subject of renewed interest because of the large quantities of this compound that are being used as an oxygenated additive in gasoline. Various studies on the fate of MTBE have shown that it can be degraded to tert-butyl formate (TBF), particularly in the atmosphere. Although it is generally recognized that TBF is subject to hydrolysis, the kinetics and products of this reaction under environmentally relevant conditions have not been described previously. In this study, we determined the kinetics of TBF hydrolysis as a function of pH and temperature. Over the pH range of 5 to 7, the neutral hydrolysis pathway predominates, with kN = (1.0 ± 0.2) × 10−6/s. Outside this range, strong pH effects were observed because of acidic and basic hydrolyses, from which we determined that kA = (2.7 ± 0.5) × 10−3/(M·s) and kB = 1.7 ± 0.3/(M·s). Buffered and unbuffered systems gave the same hydrolysis rates for a given pH, indicating that buffer catalysis was not significant under the conditions tested. The activation energies corresponding to kN, kA, and kBwere determined to be 78 ± 5, 59 ± 4, and 88 ±11 kJ/mol, respectively. In all experiments, tert-butyl alcohol was found at concentrations corresponding to stoichiometric formation from TBF. Based on our kinetics data, the expected half-life for hydrolysis of TBF at pH = 2 and 4°C (as per some standard preservation protocols for water sampling) is 6 h. At neutral pH and 22°C, the estimated half-life is 5 d, and at pH = 11 and 22°C, the value is only 8 min.

40 CFR 60.707 - Chemicals affected by subpart RRR.

Code of Federal Regulations, 2012 CFR

2012-07-01

...-7 Brometone 76-08-4 1,3-Butadiene 106-99-0 Butadiene and butene fractions n-Butane 106-97-8 1,4-Butanediol 110-63-4 Butanes, mixed 1-Butene 106-98-9 2-Butene 25167-67-3 Butenes, mixed n-Butyl acetate 123-86-4 Butyl acrylate 141-32-2 n-Butyl alcohol 71-36-3 sec-Butyl alcohol 78-92-2 tert-Butyl alcohol 75...

40 CFR 60.707 - Chemicals affected by subpart RRR.

Code of Federal Regulations, 2010 CFR

2010-07-01

...-7 Brometone 76-08-4 1,3-Butadiene 106-99-0 Butadiene and butene fractions n-Butane 106-97-8 1,4-Butanediol 110-63-4 Butanes, mixed 1-Butene 106-98-9 2-Butene 25167-67-3 Butenes, mixed n-Butyl acetate 123-86-4 Butyl acrylate 141-32-2 n-Butyl alcohol 71-36-3 sec-Butyl alcohol 78-92-2 tert-Butyl alcohol 75...

40 CFR 60.707 - Chemicals affected by subpart RRR.

Code of Federal Regulations, 2011 CFR

2011-07-01

...-7 Brometone 76-08-4 1,3-Butadiene 106-99-0 Butadiene and butene fractions n-Butane 106-97-8 1,4-Butanediol 110-63-4 Butanes, mixed 1-Butene 106-98-9 2-Butene 25167-67-3 Butenes, mixed n-Butyl acetate 123-86-4 Butyl acrylate 141-32-2 n-Butyl alcohol 71-36-3 sec-Butyl alcohol 78-92-2 tert-Butyl alcohol 75...

Reversed-phase single drop microextraction followed by high-performance liquid chromatography with fluorescence detection for the quantification of synthetic phenolic antioxidants in edible oil samples.

PubMed

Farajmand, Bahman; Esteki, Mahnaz; Koohpour, Elham; Salmani, Vahid

2017-04-01

The reversed-phase mode of single drop microextraction has been used as a preparation method for the extraction of some phenolic antioxidants from edible oil samples. Butylated hydroxyl anisole, tert-butylhydroquinone and butylated hydroxytoluene were employed as target compounds for this study. High-performance liquid chromatography followed by fluorescence detection was applied for final determination of target compounds. The most interesting feature of this study is the application of a disposable insulin syringe with some modification for microextraction procedure that efficiently improved the volume and stability of the solvent microdrop. Different parameters such as the type and volume of solvent, sample stirring rate, extraction temperature, and time were investigated and optimized. Analytical performances of the method were evaluated under optimized conditions. Under the optimal conditions, relative standard deviations were between 4.4 and 10.2%. Linear dynamic ranges were 20-10 000 to 2-1000 μg/g (depending on the analytes). Detection limits were 5-670 ng/g. Finally, the proposed method was successfully used for quantification of the antioxidants in some edible oil samples prepared from market. Relative recoveries were achieved from 88 to 111%. The proposed method had a simplicity of operation, low cost, and successful application for real samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoelectrochemical determination of tert-butylhydroquinone in edible oil samples employing CdSe/ZnS quantum dots and LiTCNE.

PubMed

Monteiro, Thatyara Oliveira; Tanaka, Auro Atsushi; Damos, Flávio Santos; Luz, Rita de Cássia Silva

2017-07-15

A novel photoelectrochemical sensor was developed for determination of tert-butyl-hydroquinone (TBHQ) in edible vegetable oils, based on CdSe/ZnS core-shell quantum dots sensitized with lithium tetracyanoethylenide (LiTCNE). The CdSe/ZnS/LiTCNE photoelectrochemical sensor presented a TBHQ photocurrent about 13-fold higher and a charge transfer resistance 62-fold lower than observed for a CdSe/ZnS sensor. The photoelectrochemical sensor showed selectivity to TBHQ, with a high photocurrent for this antioxidant compared to the photocurrent responses for other phenolic antioxidants. The CdSe/ZnS/LiTCNE photoelectrochemical sensor presented a linear range from 0.6 to 250μmolL -1 , sensitivity of 0.012μALμmol -1 , and a limit of detection of 0.21μmolL -1 for TBHQ, under optimized experimental conditions. The sensor was successfully employed in the analysis of edible oil samples, with recoveries of between 98.25% and 99.83% achieved. Copyright © 2017 Elsevier Ltd. All rights reserved.

Formation of Germa-ketenimine on the Ge(100) Surface by Adsorption of tert-Butyl Isocyanide.

PubMed

Shong, Bonggeun; Yoo, Jong Suk; Sandoval, Tania E; Bent, Stacey F

2017-06-28

Reactions of the (100) surfaces of Ge and Si with organic molecules have been generally understood within the concept of "dimers" formed by the 2 × 1 surface reconstruction. In this work, the adsorption of tert-butyl isocyanide on the Ge(100)-2 × 1 surface at large exposures is investigated under ultrahigh vacuum conditions. A combination of infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption experiments along with dispersion-corrected density functional theory calculations is used to determine the surface products. Upon adsorption of a dense monolayer of tert-butyl isocyanide, a product whose structure resembles a germa-ketenimine (N=C=Ge) with σ donation toward and π back-donation from the Ge(100) surface appears. Formation of this structure involves divalent-type surface Ge atoms that arise from cleavage of the Ge(100)-2 × 1 surface dimers. Our results reveal an unprecedented class of reactions of organic molecules at the Ge(100) surface.

Vibrational and reorientationl relaxation in liquid tert-butyl bromide and tert-butyl bromide- d9

NASA Astrophysics Data System (ADS)

Szostak, R.; Hawranek, J. P.

1992-12-01

The vibrational and reorientational correlation functions of the ν s(CBr) mode in liquid tert-butyl bromide (TBBr) and in its deuterated analogue (TBBr- d9) were determined from Raman bandshapes. The Kubo product δτ m obtained by fitting the Rothschild equation to experimental data amounts to 0.36-0.45 for the studied bands, which indicates a fairly fast modulation regime in these systems. The approximation of experimental rotational correlation functions with the help of the J-diffusion model yields values of 0.11-0.12ps for the angular momentum correlation time. The second-order rotational correlation times (1.7-2.0ps) agree well with the NMR results of D.W. Aksnes, K. Ramstad and O.P. Björlykke, Magn. Reson. Chem., 25 (1987) 1063. Selected bandshape parameters for δ(CCC) in both compounds, ϱ(CH 3) in TBBr and ν s(CC) in TBBR- d9 were also quoted.

Exceptionally long-lived light-emitting electrochemical cells: multiple intra-cation π-stacking interactions in [Ir(C^N)2(N^N)][PF6] emitters† †Electronic supplementary information (ESI) available: Experimental details. Fig. S1–S10: additional structural and NMR spectroscopic figures; voltage vs. time plots for LEC devices and electroluminescence spectra. CCDC 1019226–1019229. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03942d

PubMed Central

Bünzli, Andreas M.; Constable, Edwin C.; Prescimone, Alessandro; Zampese, Jennifer A.; Longo, Giulia; Gil-Escrig, Lidón; Pertegás, Antonio; Ortí, Enrique

2015-01-01

A series of cyclometalated iridium(iii) complexes [Ir(C^N)2(N^N)][PF6] (N^N = 2,2′-bipyridine (1), 6-phenyl-2,2′-bipyridine (2), 4,4′-di-tert-butyl-2,2′-bipyridine (3), 4,4′-di-tert-butyl-6-phenyl-2,2′-bipyridine (4); HC^N = 2-(3-phenyl)phenylpyridine (HPhppy) or 2-(3,5-diphenyl)phenylpyridine (HPh2ppy)) are reported. They have been synthesized using solvento precursors so as to avoid the use of chlorido-dimer intermediates, chloride ion contaminant being detrimental to the performance of [Ir(C^N)2(N^N)][PF6] emitters in light-electrochemical cell (LEC) devices. Single crystal structure determinations and variable temperature solution 1H NMR spectroscopic data confirm that the pendant phenyl domains engage in multiple face-to-face π-interactions within the coordination sphere of the iridium(iii) centre. The series of [Ir(Phppy)2(N^N)]+ and [Ir(Ph2ppy)2(N^N)]+ complexes investigated include those with and without intra-cation face-to-face π-stacking. All the complexes display excellent luminescent properties, in particular when employed in thin solid films. The most important observation is that all the LECs using the [Ir(Phppy)2(N^N)]+ and [Ir(Ph2ppy)2(N^N)]+ emitters (i.e. with and without intra-cation π-stacking interactions) exhibit very stable luminance outputs over time, even when driven at elevated current densities. The most stable LEC had an extrapolated lifetime of more than 2500 hours under accelerated testing conditions. PMID:29142683

Development and performance of a 129-GHz dynamic nuclear polarizer in an ultra-wide bore superconducting magnet

PubMed Central

Lumata, Lloyd L.; Martin, Richard; Jindal, Ashish K.; Kovacs, Zoltan; Conradi, Mark S.

2014-01-01

Objective We sought to build a dynamic nuclear polarization system for operation at 4.6 T (129 GHz) and evaluate its efficiency in terms of 13C polarization levels using free radicals that span a range of ESR linewidths. Materials and methods A liquid helium cryostat was placed in a 4.6 T superconducting magnet with a 150-mm warm bore diameter. A 129-GHz microwave source was used to irradiate 13C enriched samples. Temperatures close to 1 K were achieved using a vacuum pump with a 453-m3/h roots blower. A hyperpolarized 13C nuclear magnetic resonance (NMR) signal was detected using a saddle coil and a Varian VNMRS console operating at 49.208 MHz. Samples doped with free radicals BDPA (1,3-bisdipheny-lene-2-phenylallyl), trityl OX063 (tris{8-carboxyl-2,2,6,6-benzo(1,2-d:4,5-d)-bis(1,3)dithiole-4-yl}methyl sodium salt), galvinoxyl ((2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy), 2,2-diphenylpicrylhydrazyl (DPPH) and 4-oxo-TEMPO (4-Oxo-2,2,6,6-tetramethyl-1-piperidinyloxy) were assayed. Microwave dynamic nuclear polarization (DNP) spectra and solid-state 13C polarization levels for these samples were determined. Results 13C polarization levels close to 50 % were achieved for [1-13C]pyruvic acid at 1.15 K using the narrow electron spin resonance (ESR) linewidth free radicals trityl OX063 and BDPA, while 10–20 % 13C polarizations were achieved using galvinoxyl, DPPH and 4-oxo-TEMPO. Conclusion At this field strength free radicals with smaller ESR linewidths are still superior for DNP of 13C as opposed to those with linewidths that exceed that of the 1H Larmor frequency. PMID:25120071

Lipid peroxidation in mice fed a choline-deficient diet as evaluated by total hydroxyoctadecadienoic acid.

PubMed

Yoshida, Yasukazu; Itoh, Nanako; Hayakawa, Mieko; Habuchi, Yoko; Inoue, Ruriko; Chen, Zhi-Hua; Cao, Jiaofei; Cynshi, Osamu; Niki, Etsuo

2006-03-01

The relevance of oxidative stress in mice fed a choline-deficient diet (CDD) was investigated in relation to the oxidative stress marker, hydroxyoctadecadienoic acid (HODE) in comparison with F2-isoprostanes. Further, the protective effects of antioxidants against oxidative damage were assessed by using HODE. We recently proposed total HODE as a biomarker for oxidative stress in vivo. Biological samples such as plasma, urine, and tissues were first reduced and then saponified to convert various oxidation products of linoleates to HODE. In the present study, this method was applied to measure oxidative damage in mice induced by CDD for 1 mo. CDD, when compared with choline-controlled diet (CCD), increased liver weight and fatty acid accumulation but the increase in body weight was less significant. Remarkable increases in HODE and 8-iso-prostaglandin F(2alpha) in liver and plasma were observed when mice were fed with the CDD for 1 mo compared with the CCD. The HODE level was about two to three orders higher than the F2-isoprostane level. This increase was decreased to the level of the CCD when alpha-tocopherol or 2,3-dihydro-5-hydroxy-4,6-di-tert-butyl-2,2-dipentylbenzofuran, a potent synthetic antioxidant, was mixed with the CDD. The stereoisomer ratio of HODE (9-and-13 (Z,E)-HODE/9-and-13 (E,E)-HODE) was decreased by CDD compared with CCD, which was spared by the addition of alpha-tocopherol and 2,3-dihydro-5-hydroxy-4,6-di-tert-butyl-2,2-dipentylbenzofuran. However, the increase in plasma glutamic-pyruvic transaminase and fatty acids in liver induced by the CDD was not recovered by any antioxidant. This study clearly demonstrated that oxidative stress was involved in fatty liver formation induced by the CDD and that HODE was a good biomarker for an oxidative stress in vivo.

RATE CONSTANTS FOR THE REACTIONS OF OH RADICALS AND CL ATOMS WITH DI-N-PROPYL ETHER AND DI-N-BUTYL ETHER AND THEIR DEUTERATED ANALOGS. (R825252)

EPA Science Inventory

Using relative rate methods, rate constants for the gas-phase reactions of OH radicals and Cl atoms with di-n-propyl ether, di-n-propyl ether-d₁₄, di-n-butyl ether and di-n-butyl ether-d₁₈ have been measured at 296 ? 2 K and atmos...

In vitro antioxidant activities of extract and oil from roselle (Hibiscus sabdariffa L.) seed against sunflower oil autoxidation.

PubMed

Nyam, K L; Teh, Y N; Tan, C P; Kamariah, L

2012-08-01

In order to overcome the stability problems of oils and fats, synthetic antioxidants such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butyl hydroquinone (TBHQ) have widespread use as food additives in many countries. Recent reports reveal that these compounds may be implicated in many health risks, including cancer and carcinogenesis. Hence, there is a move towards the use of natural antioxidants of plant origin to replace these synthetic antioxidants. In this study, roselle seed oil (RSO) and extract (RSE) were mixed with sunflower oil, respectively to monitor degradation rate and investigate antioxidant activity during accelerated storage. The antioxidant activity was found to stabilise sunflower oil of various samples and in the order of RSE>RSO>tocopherol>sunflower oil. The total percentage increased after 5 days of storage period in free fatty acid (FFA), peroxide value (PV) and anisidine value (AV). Total oxidation value (TOx) of sunflower oil supplemented with 1500 ppm RSE was 33.3%, 47.7%, 14.5%, and 45.5%, respectively. While the total percentage increased under different analysis methods, sunflower oil supplemented with 5% RSO was 17.2%, 60.4%, 36.2% and 59.0% in the order of FFA, PV, AV and TOTOX. Both RSO and RSE were found to be more effective in stabilisation of sunflower oil compared to tocopherol. Total phenolic content of RSE was 46.40 +/- 1.51 mg GAE/100g of oil while RSO was 12.51 +/- 0.15 mg GAE/ 100g of oil. The data indicates that roselle seed oil and seed extract are rich in phenolics and antioxidant activities and may be a potential source of natural antioxidants.

Cyclic cooperative intramolecular hydrogen bond in p-tert-butylcalix[6]arene according to FTIR spectroscopy and DFT studies

NASA Astrophysics Data System (ADS)

Furer, V. L.; Potapova, L. I.; Kovalenko, V. I.

2017-06-01

This article describes a comparative research of IR spectra and H-bonds in the p-tert-butylcalix[6]arene (TB6) and calix[6]arene (C6). IR spectra were computed for compressed cone conformation by DFT method. The assignment of the bands in the IR spectra of the TB6 and C6 was made. The effect of the bulky tert-butyl substituents on the structure and H-bonding in TB6 was established. Our research has shown that in TB6 and C6 the cyclic H-bond is realized, which ensures the existence of a compressed cone conformation. Introduction of tert-butyl substituents in TB6 leads to hardening of H-bonds. Examination of IR spectra showed that when heated TB6 remains in a compressed cone conformation. In a molecule of TB6 and C6 oxygen atoms are in a ;boat; conformation.

Synthesis and evaluation of L-cystathionine as a standard for amino acid analysis.

PubMed

Amino, Yusuke; Suzuki, Yumiko

2017-01-01

L-Cystathionine is a key nonprotein amino acid related to metabolic conditions. The quantitative determination of L-cystathionine in physiological fluids by amino acid analysis is important for clinical diagnosis; however, certified reference material for L-cystathionine with satisfactory purity, content, and quantity has been unavailable until recently. Consequently, a practical and simple method for the preparation of L-cystathionine was examined, which involves thioalkylation of N-tert-butoxycarbonyl-L-cysteine tert-butyl ester, derived from L-cystine, with (2S)-2-(tert-butoxycarbonyl)amino-4-iodobutanoic acid tert-butyl ester, derived from L-aspartic acid, to obtain L-cystathionine with protecting groups, followed by single-step deprotection under mild conditions. This method produces L-cystathionine in high purity (99.4%) and having sufficient percentage content according to amino acid analysis, which could be used as a standard for the amino acid analysis of physiological fluids.

Emulsion Polymerization of Butyl Acrylate: Spin Trapping and EPR Study

NASA Technical Reports Server (NTRS)

Kim, S.; Westmoreland, D.

1994-01-01

The propagating radical in the emulsion polymerization reaction of butyl acrylate was detected by Electron Paramagnetic Resonance spectroscopy using two spin trapping agents, 2-methyl-2nitrosopropane and alpha -N-tert-butylnitrone.

μ-Carbonato-κ(4) O,O':O',O''-bis-{[2'-(di-tert-butyl-phosphan-yl)biphenyl-2-yl-κ(2) P,C (1)]palladium(II)} dichloro-methane monosolvate.

PubMed

Muller, Alfred; Holzapfel, Cedric W

2012-12-01

The title compound, [(μ2-CO3){Pd(P(t-C4H9)2(C12H8)}2]·CH2Cl2, the first CO3-bridged palladium dimer complex reported to date, was obtained while preparing the Pd(0) complex with (2-biphen-yl)P( (t) Bu)2. In the crystal, each palladium dimer is accompanied by a dichloro-methane solvent mol-ecule. Coordination of the carbonate and chelated phosphane ligands gives distorted square-planar environments at the Pd atoms. Important geometrical parameters include Pd-P(av.) = 2.2135 (4) Å, Pd-C(av.) = 1.9648 (16) Å and P-Pd-C = 84.05 (5) and 87.98 (5)°, and O-Pd-O' = 60.56 (4) and 61.13 (4)°. Bonding with the carbonate O atoms shows values of 2.1616 (11) and 2.1452 (11) Å for the Pd-O-Pd bridge, whereas other Pd-O distances are slightly longer at 2.2136 (11) and 2.1946 (11) Å. One of the tert-butyl groups is disordered over two set of sites with an occupancy ratio of 0.723 (6):0.277 (6). Weak C-H⋯O interactions are observed propagating the molecules along the [100] direction.

μ-Carbonato-κ4 O,O′:O′,O′′-bis­{[2′-(di-tert-butyl­phosphan­yl)biphenyl-2-yl-κ2 P,C 1]palladium(II)} dichloro­methane monosolvate

PubMed Central

Muller, Alfred; Holzapfel, Cedric W.

2012-01-01

The title compound, [(μ2-CO3){Pd(P(t-C4H9)2(C12H8)}2]·CH2Cl2, the first CO3-bridged palladium dimer complex reported to date, was obtained while preparing the Pd0 complex with (2-biphen­yl)P(tBu)2. In the crystal, each palladium dimer is accompanied by a dichloro­methane solvent mol­ecule. Coordination of the carbonate and chelated phosphane ligands gives distorted square-planar environments at the Pd atoms. Important geometrical parameters include Pd—P(av.) = 2.2135 (4) Å, Pd—C(av.) = 1.9648 (16) Å and P—Pd—C = 84.05 (5) and 87.98 (5)°, and O—Pd—O′ = 60.56 (4) and 61.13 (4)°. Bonding with the carbonate O atoms shows values of 2.1616 (11) and 2.1452 (11) Å for the Pd—O—Pd bridge, whereas other Pd—O distances are slightly longer at 2.2136 (11) and 2.1946 (11) Å. One of the tert-butyl groups is disordered over two set of sites with an occupancy ratio of 0.723 (6):0.277 (6). Weak C—H⋯O interactions are observed propagating the molecules along the [100] direction. PMID:23468771

Chiral 2-Aminobenzimidazole as Bifunctional Catalyst in the Asymmetric Electrophilic Amination of Unprotected 3-Substituted Oxindoles.

PubMed

Benavent, Llorenç; Baeza, Alejandro; Freckleton, Megan

2018-06-06

The use of readily available chiral trans -cyclohexanediamine-benzimidazole derivatives as bifunctional organocatalysts in the asymmetric electrophilic amination of unprotected 3-substituted oxindoles is presented. Different organocatalysts were evaluated; the most successful one contained a dimethylamino moiety ( 5 ). With this catalyst under optimized conditions, different oxindoles containing a wide variety of substituents at the 3-position were aminated in good yields and with good to excellent enantioselectivities using di- tert -butylazodicarboxylate as the aminating agent. The procedure proved to be also efficient for the amination of 3-substituted benzofuranones, although with moderate results. A bifunctional role of the catalyst, acting as Brønsted base and hydrogen bond donor, is proposed according to the experimental results observed.

Enterovirus inhibitory activity of C-8-tert-butyl substituted 4-aryl-6,7,8,9-tetrahydrobenzo[4,5]thieno[3,2-e][1,2,4]triazolo[4,3-a]pyrimidin-5(4H)-ones.

PubMed

Kumar Biswas, Bishyajit; Malpani, Yashwardhan R; Ha, Neul; Kwon, Do-Hyun; Soo Shin, Jin; Kim, Hae-Soo; Kim, Chonsaeng; Bong Han, Soo; Lee, Chong-Kyo; Jung, Young-Sik

2017-08-01

Members of a series of 4-aryl-6,7,8,9-tetrahydrobenzo[4,5]thieno[3,2-e][1,2,4]triazolo[4,3-a]pyrimidin-5(4H)-ones (1, Fig. 2) were prepared and tested against representative enteroviruses including Human Coxsackievirus B1 (Cox B1), Human Coxsackievirus B3 (Cox B3), human Poliovirus 3 (PV3), human Rhinovirus 14 (HRV14), human Rhinovirus 21 (HRV 21) and human Rhinovirus 71 (HRV 71). The C-8-tert-butyl group on the tetrahydrobenzene ring in these substances was found to be crucial for their enterovirus activity. One member of this group, 1e, showed single digit micromolar activities (1.6-8.85μM) against a spectrum of viruses screened, and the highest selectivity index (SI) values for Cox B1 (>11.2), for Cox B3 (>11.5), and for PV3 (>51.2), respectively. In contrast, 1p, was the most active analog against the selected HRVs (1.8-2.6μM), and showed the highest selectivity indices among the group of compounds tested. The SI values for 1p were 11.5 for HRV14, 8.4 for HRV21, and 12.1 for HRV71, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Extreme oxatriquinanes and a record C-O bond length

NASA Astrophysics Data System (ADS)

Gunbas, Gorkem; Hafezi, Nema; Sheppard, William L.; Olmstead, Marilyn M.; Stoyanova, Irini V.; Tham, Fook S.; Meyer, Matthew P.; Mascal, Mark

2012-12-01

Oxatriquinanes are fused, tricyclic oxonium ions that are known to have exceptional stability compared to simple alkyl oxonium salts. C-O bonds in ethers are generally ˜1.43 Å in length, but oxatriquinane has been found to have C-O bond lengths of 1.54 Å. A search of the Cambridge Structural Database turned up no bona fide C-O bond length exceeding this value. Computational modelling of oxatriquinane alongside other alkyl oxonium ions indicated that the electronic consequences of molecular strain were primarily responsible for the observed bond elongation. We also show that substitution of the oxatriquinane ring system with alkyl groups of increasing steric demand pushes the C-O bond to unheard of distances, culminating in a tert-butyl derivative at a predicted 1.60 Å. Chemical synthesis and an X-ray crystallographic study of these compounds validated the results of the modelling work and, finally, an extraordinary 1.622 Å C-O bond was observed in 1,4,7-tri-tert-butyloxatriquinane.

Synthesis and Larvicidal Activity of Novel Thenoylhydrazide Derivatives

NASA Astrophysics Data System (ADS)

Song, Gao-Peng; Hu, De-Kun; Tian, Hao; Li, Ya-Sheng; Cao, Yun-Shen; Jin, Hong-Wei; Cui, Zi-Ning

2016-03-01

A pair of chemical isomeric structures of novel N-tert-butylphenyl thenoylhydrazide compounds I and II were designed and synthesized. Their structures were characterized by MS, IR, 1H NMR, elemental analysis and X-ray single crystal diffraction. The regioselectivity of the Meerwein arylation reaction and the electrophilic substitution reaction of N-tert-butyl hydrazine were studied by density functional theory (DFT) quantum chemical method. The larvicidal tests revealed that some compounds I had excellent larvicidal activity against Culex pipiens pallens. As the candidates of insect growth regulators (IGRs), the larval growth inhibition and regulation against Culex pipiens pallens were examined for some compounds, especially I1 and I7. Compounds I1 and I7 were further indicated as an ecdysteroid agonist by reporter gene assay on the Spodoptera frugiperda cell line (Sf9 cells). Finally, a molecular docking study of compound I7 was conducted, which was not only beneficial to understand the structure-activity relationship, but also useful for development of new IGRs for the control of mosquitos.

N-tert-Butyl-N'-(5,7-dimethyl-1,8-naphthyridin-2-yl)urea.

PubMed

Lüning, U; Kühl, C; Bolte, M

2001-08-01

The title compound, C(15)H(20)N(4)O, has been synthesized as an AADD recognition unit for quadruple hydrogen bonds. All non-H atoms of the molecule apart from two methyl groups of the tert-butyl group lie in a common plane. An intramolecular hydrogen bond is formed connecting two N atoms. In the solid state, the title compound crystallizes as a centrosymmetric dimer connected by N-H...O=C interactions with an N...O distance of 2.824 (2) A.

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

West, Brian H.; Connatser, Raynella M.; Lewis, Samuel Arthur

The Fuels, Engines, and Emissions Research Center completed analysis and testing of the CPS Powershot gasoline additive under the auspices of the Department of Energy’s Technical Assistance for US Small Businesses in Vehicle Technologies. Gas chromatography-mass spectrometry (GC-MS) was used to quantify the makeup of the additive, finding a predominance of 2,3-Ditert-Butoxypropanol, also known as Glyceryl Di-Tert-Butyl Ether (GTBE). Blends of the additive at 2 and 4 volume percent were subjected to a number of standard ASTM tests, including Research Octane Number, Motor Octane Number, distillation, and vapor pressure. Results show a high boiling range and low vapor pressure formore » the additive, and a very modest octane boosting effect in gasoline with and without ethanol.« less

High temperature concrete composites containing organosiloxane crosslinked copolymers

DOEpatents

Zeldin, Arkady; Carciello, Neal; Kukacka, Lawrence; Fontana, Jack

1980-01-01

This invention relates to high temperature polymer concrete composites comprising about 10-30% by weight of a liquid monomer mixture consisting essentially of an organosiloxane polymer crosslinked with an olefinically unsaturated monomer selected from the group consisting of styrene, methyl methacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, n-phenylmalimide, divinyl benzene and mixtures theroef; and about 70-90% by weight of an inert inorganic filler system containing silica sand and preferably a member selected from the group consisting of portland cement, Fe.sub.2 O.sub.3, carbon black and mixtures thereof; and optionally a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide and other organic peroxides to initiate crosspolymerization of the monomer mixture in the presence of the inorganic filler.

Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase.

PubMed

Kim, In-Hae; Park, Yong-Kyu; Nishiwaki, Hisashi; Hammock, Bruce D; Nishi, Kosuke

2015-11-15

Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase (sEH) were investigated. First, a series of alkyl or aryl groups were substituted on the carbon alpha to the phosphonate function in amide compounds to see whether substituted phosphonates can act as a secondary pharmacophore. A tert-butyl group (16) on the alpha carbon was found to yield most potent inhibition on the target enzyme. A 4-50-fold drop in inhibition was induced by other substituents such as aryls, substituted aryls, cycloalkyls, and alkyls. Then, the modification of the O-substituents on the phosphonate function revealed that diethyl groups (16 and 23) were preferable for inhibition to other longer alkyls or substituted alkyls. In amide compounds with the optimized diethylphosphonate moiety and an alkyl substitution such as adamantane (16), tetrahydronaphthalene (31), or adamantanemethane (36), highly potent inhibitions were gained. In addition, the resulting potent amide-phosphonate compounds had reasonable water solubility, suggesting that substituted phosphonates in amide inhibitors are effective for both inhibition potency on the human sEH and water solubility as a secondary pharmacophore. Copyright © 2015 Elsevier Ltd. All rights reserved.

N-[2-(2,2-Di-methyl-propanamido)-pyrimidin-4-yl]-2,2-di-methyl-propanamide n-hexane 0.25-solvate hemihydrate.

PubMed

Ośmiałowski, Borys; Valkonen, Arto; Chęcińska, Lilianna

2013-10-05

The asymmetric unit of the title compound, C14H22N4O2·0.25C6H14·0.5H2O, contains two independent mol-ecules of 2,4-bis-(pivaloyl-amino)-pyrimidine (M) with similar conformations, one water mol-ecule and one-half n-hexane solvent mol-ecule situated on an inversion center. In one independent M mol-ecule, one of the two tert-butyl groups is rotationally disordered between two orientations in a 3:2 ratio. The n-hexane solvent mol-ecule is disordered between two conformations in the same ratio. The water mol-ecule bridges two independent M mol-ecules via O-H⋯O, N-H⋯O and O-H⋯N hydrogen bonds into a 2M·H2O unit, and these units are further linked by N-H⋯N hydrogen bonds into chains running in the [010] direction. Weak C-H⋯O inter-actions are observed between the adjacent chains.

Equilibrium Polymerization of Butyl Methacrylate in Bulk and in Nanopore Confinement

NASA Astrophysics Data System (ADS)

Tian, Qian; Simon, Sindee

The equilibrium between monomer and polymer in free radical polymerization can be shifted towards monomer under nanoconfinement. This decrease in ceiling temperature is due to a decrease in the entropy associated with the constrained polymer chains, resulting in a larger negative change in entropy of reaction. Here, we investigate the equilibrium polymerization of butyl methacrylate (BMA) in bulk and in nanopore confinement with differential scanning calorimetry (DSC) using di-tert-butyl peroxide (DTBP) as initiator. This system has several advantages compare to the previously studied system of methyl methacrylate (MMA) initiated with 2,2'-azo-bis-isobutyronitrile (AIBN), namely, a reduced rate of reaction, higher boiling point of monomer, and higher initiator utilization temperature range, all of which facilitate the study of the reaction at high temperatures near the ceiling temperature. Interestingly, for BMA, there is no change in limiting conversion between material reacted in bulk and that in controlled pore glass having pore diameters of 7.5 and 50 nm. This unexpected result may be due to the greater flexibility of the PBMA chains compared to PMMA, suggesting that in the BMA/PBMA system, the degree of confinement is relatively low. Future studies will continue to investigate how the entropy change on reaction is affected by confinement.

Pre-treatment with the synthetic antioxidant T-butyl bisphenol protects cerebral tissues from experimental ischemia reperfusion injury.

PubMed

Duong, Thi Thuy Hong; Chami, Belal; McMahon, Aisling C; Fong, Genevieve M; Dennis, Joanne M; Freedman, Saul B; Witting, Paul K

2014-09-01

Treatments to inhibit or repair neuronal cell damage sustained during focal ischemia/reperfusion injury in stroke are largely unavailable. We demonstrate that dietary supplementation with the antioxidant di-tert-butyl-bisphenol (BP) before injury decreases infarction and vascular complications in experimental stroke in an animal model. We confirm that BP, a synthetic polyphenol with superior radical-scavenging activity than vitamin E, crosses the blood-brain barrier and accumulates in rat brain. Supplementation with BP did not affect blood pressure or endogenous vitamin E levels in plasma or cerebral tissue. Pre-treatment with BP significantly lowered lipid, protein and thiol oxidation and decreased infarct size in animals subjected to middle cerebral artery occlusion (2 h) and reperfusion (24 h) injury. This neuroprotective action was accompanied by down-regulation of hypoxia inducible factor-1α and glucose transporter-1 mRNA levels, maintenance of neuronal tissue ATP concentration and inhibition of pro-apoptotic factors that together enhanced cerebral tissue viability after injury. That pre-treatment with BP ameliorates oxidative damage and preserves cerebral tissue during focal ischemic insult indicates that oxidative stress plays at least some causal role in promoting tissue damage in experimental stroke. The data strongly suggest that inhibition of oxidative stress through BP scavenging free radicals in vivo contributes significantly to neuroprotection. We demonstrate that pre-treatment with ditert-butyl bisphenol(Di-t-Bu-BP) inhibits lipid, protein, and total thiol oxidation and decreases caspase activation and infarct size in rats subjected to middle cerebral artery occlusion (2 h) and reperfusion (24 h) injury. These data suggest that inhibition of oxidative stress contributes significantly to neuroprotection. © 2014 International Society for Neurochemistry.

n-Alkane assimilation and tert-butyl alcohol (TBA) oxidation capacity in Mycobacterium austroafricanum strains.

PubMed

Lopes Ferreira, Nicolas; Mathis, Hugues; Labbé, Diane; Monot, Frédéric; Greer, Charles W; Fayolle-Guichard, Françoise

2007-06-01

Mycobacterium austroafricanum IFP 2012, which grows on methyl tert-butyl ether (MTBE) and on tert-butyl alcohol (TBA), the main intermediate of MTBE degradation, also grows on a broad range of n-alkanes (C2 to C16). A single alkB gene copy, encoding a non-heme alkane monooxygenase, was partially amplified from the genome of this bacterium. Its expression was induced after growth on n-propane, n-hexane, n-hexadecane and on TBA but not after growth on LB. The capacity of other fast-growing mycobacteria to grow on n-alkanes (C1 to C16) and to degrade TBA after growth on n-alkanes was compared to that of M. austroafricanum IFP 2012. We studied M. austroafricanum IFP 2012 and IFP 2015 able to grow on MTBE, M. austroafricanum IFP 2173 able to grow on isooctane, Mycobacterium sp. IFP 2009 able to grow on ethyl tert-butyl ether (ETBE), M. vaccae JOB5 (M. austroaafricanum ATCC 29678) able to degrade MTBE and TBA and M. smegmatis mc2 155 with no known degradation capacity towards fuel oxygenates. The M. austroafricanum strains grew on a broad range of n-alkanes and three were able to degrade TBA after growth on propane, hexane and hexadecane. An alkB gene was partially amplified from the genome of all mycobacteria and a sequence comparison demonstrated a close relationship among the M. austroafricanum strains. This is the first report suggesting the involvement of an alkane hydroxylase in TBA oxidation, a key step during MTBE metabolism.

Anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA).

PubMed

Finneran, K T; Lovley, D R

2001-05-01

The potential for anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) was investigated in laboratory incubations of sediments from a petroleum-contaminated aquifer and in aquatic sediments. The addition of humic substances (HS) stimulated the anaerobic degradation of MTBE in aquifer sediments in which Fe(III) was available as an electron acceptor. This is attributed to the fact that HS and other extracellular quinones can stimulate the activity of Fe(III)-reducing microorganisms by acting as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides. MTBE was not degraded in aquifer sediments without Fe(III) and HS. [14C]-MTBE added to aquatic sediments adapted for anaerobic MTBE degradation was converted to 14CO2 in the presence or absence of HS or the HS analog, anthraquione-2,6-disulfonate. Unamended aquatic sediments produced 14CH4 as well as 14CO2 from [14C]-MTBE. The aquatic sediments also rapidly consumed TBA under anaerobic conditions and converted [14C]-TBA to 14CH4 and 14CO2. An adaptation period of ca. 250-300 days was required prior to the most rapid anaerobic MTBE degradation in both sediment types, whereas TBA was metabolized in the aquatic sediments without a lag. These results demonstrate that, under the appropriate conditions, MTBE and TBA can be degraded in the absence of oxygen. This suggests that it may be possible to design strategies for the anaerobic remediation of MTBE in petroleum-contaminated subsurface environments.

METHYL TERT-BUTYLETHER-WATER INTERACTION

EPA Science Inventory

Methyl tert-butyl ether (MTBE) is a well-known environmental contaminant owing to its high solubility in water. Since the early 1990s, MTBE has been added to gasoline to improve air quality in some metropolitan areas of the United States. Improved air quality was, however, achiev...

Remote Steric Effect as a Facile Strategy for Improving the Efficiency of Exciplex-Based OLEDs.

PubMed

Hung, Wen-Yi; Wang, Ting-Chih; Chiang, Pin-Yi; Peng, Bo-Ji; Wong, Ken-Tsung

2017-03-01

This work reports a new strategy of introducing remote steric effect onto the electron donor for giving the better performance of the exciplex-based organic light-emitting device (OLED). The bulky triphenylsilyl group (SiPh 3 ) was introduced onto the fluorene bridge of 4,4'-(9H-fluorene-9,9-diyl)bis(N,N-di-p-tolylaniline) (DTAF) to create remote steric interactions for increasing the possibility of effective contacts between electron-donating chromophores and acceptor molecules, rendering the resulting exciplex to have a higher photoluminescence quantum yield (PLQY). The green exciplex device based on DSDTAF:3N-T2T (1:1) as an emitting layer exhibits a low turn-on voltage of 2.0 V, high maximum efficiencies (13.2%, 42.9 cd A -1 , 45.5 lm W -1 ), which are higher than the device employed DTAF (without SiPh 3 groups) (11.6%, 35.3 cd A -1 , 41.3 lm W -1 ) as donor under the same device structure. This strategy was further examined for blue exciplex, where the EQE was enhanced from 9.5% to 12.5% as the electron acceptor PO-T2T mixed with a tert-butyl group substituted carbazole-based donor (CPTBF) as the emitting exciplex in device. This strategy is simple and useful for developing high performance exciplex OLEDs.

40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Butyl acrylate, polymer with... NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.6920 Butyl... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane...

2-(4-Bromo­benz­yl)-5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra­methoxy­calix[4]arene

PubMed Central

Fischer, Conrad; Lin, Guisheng; Seichter, Wilhelm; Weber, Edwin

2009-01-01

In the title compound, C55H69BrO4, the calixarene mol­ecule displays a ‘partial cone’ conformation bearing the lateral substituent in a sterically favorable equatorial arrangement between two syn-orientated arene units. The crystal packing is stabilized by weak C—H⋯π contacts, involving one tert-butyl group, and π–stacking inter­actions of the lateral bromo­benzene units [centroid–centroid distance = 3.706 (1) Å]. PMID:21582956

Overview of technologies for removal of methyl tert-butyl ether (MTBE) from water.

PubMed

Levchuk, Irina; Bhatnagar, Amit; Sillanpää, Mika

2014-04-01

Wide use of methyl tert-butyl ether (MTBE) as fuel oxygenates leads to worldwide environment contamination with this compound basically due to fuel leaks from storage or pipelines. Presence of MTBE in drinking water is of high environmental and social concern. Existing methods for MTBE removal from water have a number of limitations which can be possibly overcome in the future with use of emerging technologies. This work aims to provide an updated overview of recent developments in technologies for MTBE removal from water. Copyright © 2014. Published by Elsevier B.V.

Synchrotron Photoionization Investigation of the Oxidation of Ethyl tert-Butyl Ether.

PubMed

Winfough, Matthew; Yao, Rong; Ng, Martin; Catani, Katherine; Meloni, Giovanni

2017-02-23

The oxidation of ethyl tert-butyl ether (ETBE), a widely used fuel oxygenated additive, is investigated using Cl atoms as initiators in the presence of oxygen. The reaction is carried out at 293, 550, and 700 K. Reaction products are probed by a multiplexed chemical kinetics photoionization mass spectrometer coupled with the synchrotron radiation produced at the Advanced Light Source (ALS) of the Lawrence Berkeley National Laboratory. Products are identified on the basis of mass-to-charge ratio, ionization energies, and shape of photoionization spectra. Reaction pathways are proposed together with detected primary products.

Novel fluoro copolymers for 157-nm photoresists: a progress report

NASA Astrophysics Data System (ADS)

Hohle, Christoph; Hien, Stefan; Eschbaumer, Christian; Rottstegge, Joerg; Sebald, Michael

2002-07-01

Several fluoro-substituted polymers consisting of acid cleavable methacryoic or cinnamic acid tert.-butyl ester compounds copolymerized with maleic acid anhydride derivatives were synthesized by radical copolymerization. Vacuum ultraviolet transmission measurements of the samples reveal absorbances down to 5micrometers -1 despite of the strongly absorbing anhydride moiety which serves as silylation anchor for the application of the Chemical Amplification of Resist Lines (CARL) process, one of the promising approaches for sub-90nm pattern fabrication. Some of the samples exhibit resolutions down to 110nm dense at 157nm exposure using an alternating phase shift mask. The feasibility of the CARL principle including the silylation reaction after development has been demonstrated with selected fluorinated polymer samples.

AVOIDING HYDROLYSIS OF FUEL ETHER OXYGENATES DURING STATIC HEADSPACE ANALYSIS

EPA Science Inventory

A headspace autosampler, gas chromatograph and ion trap mass spectrometer (headspace GC/MS) were used for trace analysis of fuel oxygenates and related compounds and aromatics in water. A method has been developed for determination of methyl tert-butyl ether (MTBE), ethyl tert-b...

IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) (Preliminary Assessment Materials)

EPA Science Inventory

In August 2013, EPA released the draft literature searches and associated search strategies, evidence tables, and exposure response arrays for TBA to obtain input from stakeholders and the public prior to developing the draft IRIS assessment. Specifically, EPA was interested in c...

40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane...

40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane...

40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane...

40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane...

Facile Rearrangement of 3-Oxoalkyl Radicals is Evident in Low-Temperature Gas-Phase Oxidation of Ketones

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

Scheer, Adam M.; Welz, Oliver; Sasaki, Darryl Y.

The pulsed photolytic chlorine-initiated oxidation of methyl-tert-butyl ketone (MTbuK), di-tert-butyl ketone (DTbuK), and a series of partially deuterated diethyl ketones (DEK) is studied in the gas phase at 8 Torr and 550–650 K. Products are monitored as a function of reaction time, mass, and photoionization energy using multiplexed photoionization mass spectrometry with tunable synchrotron ionizing radiation. The results establish that the primary 3-oxoalkyl radicals of those ketones, formed by abstraction of a hydrogen atom from the carbon atom in γ-position relative to the carbonyl oxygen, undergo a rapid rearrangement resulting in an effective 1,2-acyl group migration, similar to that inmore » a Dowd–Beckwith ring expansion. Without this rearrangement, peroxy radicals derived from MTbuK and DTbuK cannot undergo HO2 elimination to yield a closed-shell unsaturated hydrocarbon coproduct. However, not only are these coproducts observed, but they represent the dominant oxidation channels of these ketones under the conditions of this study. For MTbuK and DTbuK, the rearrangement yields a more stable tertiary radical, which provides the thermodynamic driving force for this reaction. Even in the absence of such a driving force in the oxidation of partially deuterated DEK, the 1,2-acyl group migration is observed. Quantum chemical (CBS-QB3) calculations show the barrier for gas-phase rearrangement to be on the order of 10 kcal mol–1. The MTbuK oxidation experiments also show several minor channels, including β-scission of the initial radicals and cyclic ether formation.« less

40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., Calcium Salt Maleic Anhydride Methacrylic Acid *Methacrylic Acid Esters Methane Methyl Ethyl Ketone Methyl Methacrylate Methyl Tert-Butyl Ether Methylisobutyl Ketone *n-Alkanes n-Butyl Alcohol n-Butylacetate n... Acid Nylon Salt Oxalic Acid *Oxo Aldehydes—Alcohols Pentaerythritol Pentane *Pentenes *Petroleum...

40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

..., Calcium Salt Maleic Anhydride Methacrylic Acid *Methacrylic Acid Esters Methane Methyl Ethyl Ketone Methyl Methacrylate Methyl Tert-Butyl Ether Methylisobutyl Ketone *n-Alkanes n-Butyl Alcohol n-Butylacetate n... Acid Nylon Salt Oxalic Acid *Oxo Aldehydes—Alcohols Pentaerythritol Pentane *Pentenes *Petroleum...

40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., Calcium Salt Maleic Anhydride Methacrylic Acid *Methacrylic Acid Esters Methane Methyl Ethyl Ketone Methyl Methacrylate Methyl Tert-Butyl Ether Methylisobutyl Ketone *n-Alkanes n-Butyl Alcohol n-Butylacetate n... Acid Nylon Salt Oxalic Acid *Oxo Aldehydes—Alcohols Pentaerythritol Pentane *Pentenes *Petroleum...

40 CFR 414.70 - Applicability; description of the bulk organic chemicals subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

..., Calcium Salt Maleic Anhydride Methacrylic Acid *Methacrylic Acid Esters Methane Methyl Ethyl Ketone Methyl Methacrylate Methyl Tert-Butyl Ether Methylisobutyl Ketone *n-Alkanes n-Butyl Alcohol n-Butylacetate n... Acid Nylon Salt Oxalic Acid *Oxo Aldehydes—Alcohols Pentaerythritol Pentane *Pentenes *Petroleum...

[Toxicity effects of phthalate substitute plasticizers used in toys].

PubMed

Hirata-Koizumi, Mutsuko; Takahashi, Mika; Matsumoto, Mariko; Kawamura, Tomoko; Ono, Atsushi; Hirose, Akihiko

2012-01-01

Phthalate esters are widely used as plasticizers in polyvinyl chloride products. Because of human health concerns, regulatory authorities in Japan, US, Europe and other countries control the use of di(2-ethylhexyl) phthalate, diisononyl phthalate, di-n-butyl phthalate, butylbenzyl phthalate, diisodecyl phthalate and di-n-octyl phthalate for the toys that can be put directly in infants' mouths. While these regulatory actions will likely reduce the usage of phthalate esters, there is concern that other plasticizers that have not been sufficiently evaluated for safety will be used more frequently. We therefore collected and evaluated the toxicological information on di(2-ethylhexyl) terephthalate (DEHT), 1,2-cyclohexanedicarboxylic acid, diisononyl ester (DINCH), diisononyl adipate (DINA), 2,2,4-trimetyl-1,3-pentanediol diisobutyrate (TXIB), tri-n-butyl citrate (TBC) and acetyl tri-n-butyl citrate (ATBC) which were detected at a relatively high frequency in toys. The collected data have shown that chronic exposure to DEHT affects the eye and nasal turbinate, and DINCH exerts effects on the thyroid and kidney in rats. DINA and TXIB have been reported to have hepatic and renal effects in dogs or rats, and ATBC slightly affected the liver in rats. The NOAELs for repeated dose toxicity are relatively low for DINCH (40 mg/kg bw/day) and TXIB (30 mg/kg bw/day) compared with DEHT, DINA and ATBC. DEHT, TXIB and ATBC have been reported to have reproductive/developmental effects at relatively high doses in rats. For DINA and TBC, available data are insufficient for assessing the hazards, and therefore, adequate toxicity studies should be conducted. In the present review, the toxicity information on 6 alternatives to phthalate plasticizers is summarized, focusing on the effects after oral exposure, which is the route of most concern.

Using DNA-Stable Isotope Probing to Identify MTBE- and TBA-Degrading Microorganisms in Contaminated Groundwater.

PubMed

Key, Katherine C; Sublette, Kerry L; Duncan, Kathleen; Mackay, Douglas M; Scow, Kate M; Ogles, Dora

2013-01-01

Although the anaerobic biodegradation of methyl tert -butyl ether (MTBE) and tert -butyl alcohol (TBA) has been documented in the laboratory and the field, knowledge of the microorganisms and mechanisms involved is still lacking. In this study, DNA-stable isotope probing (SIP) was used to identify microorganisms involved in anaerobic fuel oxygenate biodegradation in a sulfate-reducing MTBE and TBA plume. Microorganisms were collected in the field using Bio-Sep® beads amended with 13 C 5 -MTBE, 13 C 1 -MTBE (only methoxy carbon labeled), or 13 C 4 -TBA. 13 C-DNA and 12 C-DNA extracted from the Bio-Sep beads were cloned and 16S rRNA gene sequences were used to identify the indigenous microorganisms involved in degrading the methoxy group of MTBE and the tert -butyl group of MTBE and TBA. Results indicated that microorganisms were actively degrading 13 C-labeled MTBE and TBA in situ and the 13 C was incorporated into their DNA. Several sequences related to known MTBE- and TBA-degraders in the Burkholderiales and the Sphingomonadales orders were detected in all three 13 C clone libraries and were likely to be primary degraders at the site. Sequences related to sulfate-reducing bacteria and iron-reducers, such as Geobacter and Geothrix , were only detected in the clone libraries where MTBE and TBA were fully labeled with 13 C, suggesting that they were involved in processing carbon from the tert -butyl group. Sequences similar to the Pseudomonas genus predominated in the clone library where only the methoxy carbon of MTBE was labeled with 13 C. It is likely that members of this genus were secondary degraders cross-feeding on 13 C-labeled metabolites such as acetate.

Sorption of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) to synthetic resins.

PubMed

Bi, Erping; Haderlein, Stefan B; Schmidt, Torsten C

2005-10-01

Methyl tert-butyl ether (MTBE) is a widely used gasoline oxygenate. Contamination of MTBE and its major degradation product tert-butyl alcohol (TBA) in groundwater and surface water has received great attention. However, sorption affinity and sorption mechanisms of MTBE and TBA to synthetic resins, which can be potentially used in removal of these contaminants from water, in passive sampling, or in enrichment of bacteria, have not been studied systemically. In this study, kinetic and equilibrium sorption experiments (single solute and binary mixtures) on four synthetic resins were conducted. The sorption affinity of the investigated sorbents for MTBE and TBA decreases in the order Ambersorb 563>Optipore L493>Amberlite XAD4>Amberlite XAD7, and all show higher sorption affinity for MTBE than for TBA. Binary experiments with o-xylene, a major compound of gasoline as co-contaminant, imply that all resins preferentially sorb o-xylene over MTBE or TBA, i.e., there is sorption competition. In the equilibrium aqueous concentration (Ceq) range (0.1-139.0 mg/L for MTBE, and 0.01-48.4 mg/L for TBA), experimental and modeling results as well as sorbent characteristics indicate that micropore filling and/or some other type of adsorption process (e.g., adsorption to specific sites of high sorption potential at low concentrations) rather than partitioning were the dominant sorption mechanisms. Optipore L493 has favourable sorption and desorption characteristics, and is a suitable sorbent, e.g., in bacteria enrichment or passive sampling for moderately polar compounds. However, for highly polar compounds such as TBA, Ambersorb 563 might be a better choice, especially in water treatment.

Using DNA-Stable Isotope Probing to Identify MTBE- and TBA-Degrading Microorganisms in Contaminated Groundwater

PubMed Central

Key, Katherine C.; Sublette, Kerry L.; Duncan, Kathleen; Mackay, Douglas M.; Scow, Kate M.; Ogles, Dora

2014-01-01

Although the anaerobic biodegradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) has been documented in the laboratory and the field, knowledge of the microorganisms and mechanisms involved is still lacking. In this study, DNA-stable isotope probing (SIP) was used to identify microorganisms involved in anaerobic fuel oxygenate biodegradation in a sulfate-reducing MTBE and TBA plume. Microorganisms were collected in the field using Bio-Sep® beads amended with 13C5-MTBE, 13C1-MTBE (only methoxy carbon labeled), or13C4-TBA. 13C-DNA and 12C-DNA extracted from the Bio-Sep beads were cloned and 16S rRNA gene sequences were used to identify the indigenous microorganisms involved in degrading the methoxy group of MTBE and the tert-butyl group of MTBE and TBA. Results indicated that microorganisms were actively degrading 13C-labeled MTBE and TBA in situ and the 13C was incorporated into their DNA. Several sequences related to known MTBE- and TBA-degraders in the Burkholderiales and the Sphingomonadales orders were detected in all three13C clone libraries and were likely to be primary degraders at the site. Sequences related to sulfate-reducing bacteria and iron-reducers, such as Geobacter and Geothrix, were only detected in the clone libraries where MTBE and TBA were fully labeled with 13C, suggesting that they were involved in processing carbon from the tert-butyl group. Sequences similar to the Pseudomonas genus predominated in the clone library where only the methoxy carbon of MTBE was labeled with 13C. It is likely that members of this genus were secondary degraders cross-feeding on 13C-labeled metabolites such as acetate. PMID:25525320

Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

NASA Astrophysics Data System (ADS)

Lalevée, J.; Fouassier, J. P.; Blanchard, N.; Ingold, K. U.

2011-07-01

Aminoalkyl radicals, such as Et2NCrad HCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCrad HCH3 reacts with CCl4 and CBr4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N+dbnd CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., rad CCl3 and rad CHCl2 (ESR, spin-trapping detection).

High temperature chemically resistant polymer concrete

DOEpatents

Sugama, T.; Kukacka, L.E.

High temperature chemically resistant, non-aqueous polymer concrete composites consist of about 12 to 20% by weight of a water-insoluble polymer binder. The binder is polymerized in situ from a liquid vinyl-type monomer or mixture of vinyl containing monomers such as triallylcyanurate, styrene, acrylonitrile, acrylamide, methacrylamide, methyl-methacrylate, trimethylolpropane trimethacrylate and divinyl benzene. About 5 to 40% by weight of a reactive inorganic filler selected from the group consisting of tricalcium silicate and dicalcium silicate and mixtures containing less than 2% free lime, and about 48 to 83% by weight of silica sand/ and a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, other orgaic peroxides and combinations to initiate polymerization of the monomer in the presence of the inorganic filers are used.

Biodegradation of di-n-Butyl Phthalate by Achromobacter sp. Isolated from Rural Domestic Wastewater.

PubMed

Jin, Decai; Kong, Xiao; Li, Yujie; Bai, Zhihui; Zhuang, Guoqiang; Zhuang, Xuliang; Deng, Ye

2015-10-26

A bacterial strain W-1, isolated from rural domestic wastewater, can utilize the environmental hormone di-n-butyl phthalate (DBP) as the sole carbon and energy source. The isolated bacterium species was confirmed to belong to the genus Achromobacter based on its 16S rRNA gene sequence. The results of substrate utilization tests showed that the strain W-1 could utilize other common phthalates and phenol. High-performance liquid chromatography analysis revealed that the optimal conditions for DBP degradation were pH 7.0, 35 °C, and an agitation rate of 175 rpm. Under these conditions, 500 mg/L of DBP was completely degraded within 30 h. The effects of heavy metals (50 mg/L Cu(2+) and 500 mg/L Pb(2+)) and surfactants (100 mg/L SDS and 500 mg/L Tween 20) on DBP degradation were investigated. The results demonstrated that Cu(2+) and SDS severely inhibited DBP degradation and Pb(2+) weakly inhibited DBP degradation, while Tween 20 greatly enhanced DBP degradation. Furthermore, phthalate degradation genes were found to be located on a plasmid present in Achromobacter sp. W-1.

21 CFR 176.200 - Defoaming agents used in coatings.

Code of Federal Regulations, 2011 CFR

2011-04-01

... alcohol tert-Butyl alcohol Butyl stearate Castor oil, sulfated, ammonium, potassium, or sodium salt Cetyl... palmitate Mineral oil Mustardseed oil, sulfated, ammonium, potassium, or sodium salt Myristyl alcohol... hydrocarbons As defined in § 178.3650 of this chapter. Oleic acid, sulfated, ammonium, potassium, or sodium...

21 CFR 176.200 - Defoaming agents used in coatings.

Code of Federal Regulations, 2010 CFR

2010-04-01

... alcohol tert-Butyl alcohol Butyl stearate Castor oil, sulfated, ammonium, potassium, or sodium salt Cetyl... palmitate Mineral oil Mustardseed oil, sulfated, ammonium, potassium, or sodium salt Myristyl alcohol... hydrocarbons As defined in § 178.3650 of this chapter. Oleic acid, sulfated, ammonium, potassium, or sodium...

Expression of an alkane monooxygenase (alkB) gene and methyl tert-butyl ether co-metabolic oxidation in Pseudomonas citronellolis.

PubMed

Bravo, Ana Luisa; Sigala, Juan Carlos; Le Borgne, Sylvie; Morales, Marcia

2015-04-01

Pseudomonas citronellolis UAM-Ps1 co-metabolically transforms methyl tert-butyl ether (MTBE) to tert-butyl alcohol with n-pentane (2.6 mM), n-octane (1.5 mM) or dicyclopropylketone (DCPK) (4.4 mM), a gratuitous inducer of alkane hydroxylase (AlkB) activity. The reverse transcription quantitative real-time PCR was used to quantify the alkane monooxygenase (alkB) gene expression. The alkB gene was expressed in the presence of n-alkanes and DCPK and MTBE oxidation occurred only in cultures when alkB was transcribed. A correlation between the number of alkB transcripts and MTBE consumption was found (ΜΤΒΕ consumption in μmol = 1.44e(-13) x DNA copies, R(2) = 0.99) when MTBE (0.84 mM) was added. Furthermore, alkB was cloned and expressed into Escherichia coli and the recombinant AlkB had a molecular weight of 42 kDa. This is the first report where the expression of alkB is related to the co-metabolic oxidation of MTBE.

Azobenzene versus 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) at Au(111): characterizing the role of spacer groups.

PubMed

McNellis, Erik R; Bronner, Christopher; Meyer, Jörg; Weinelt, Martin; Tegeder, Petra; Reuter, Karsten

2010-06-28

We present large-scale density-functional theory (DFT) calculations and temperature programmed desorption measurements to characterize the structural, energetic and vibrational properties of the functionalized molecular switch 3,3',5,5'-tetra-tert-butyl-azobenzene (TBA) adsorbed at Au(111). Particular emphasis is placed on exploring the accuracy of the semi-empirical dispersion correction approach to semi-local DFT (DFT-D) in accounting for the substantial van der Waals component in the surface bonding. In line with previous findings for benzene and pure azobenzene at coinage metal surfaces, DFT-D significantly overbinds the molecule, but seems to yield an accurate adsorption geometry as far as can be judged from the experimental data. Comparing the trans adsorption geometry of TBA and azobenzene at Au(111) reveals a remarkable insensitivity of the structural and vibrational properties of the -N[double bond, length as m-dash]N- moiety. This questions the established view of the role of the bulky tert-butyl-spacer groups for the switching of TBA in terms of a mere geometric decoupling of the photochemically active diazo-bridge from the gold substrate.

EFFECT OF BTEX ON THE DEGRADATION OF MTBE AND TBA BY MIXED BACTERIAL CONSORTIUM

EPA Science Inventory

Methyl tert-butyl ether (MTBE) contamination in groundwater often coexists with benzene, toluene, ethylbenzene, and xylene (BTEX) near the source of the plume. Tertiary butyl alcohol (TBA) is a prevalent intermediate of MTBE degradation. Therefore, there is a significant p...

An X-ray crystallographic and density functional theory study of (3Z)-4-(5-ethylsulfonyl-2-hydroxyanilino)pent-3-en-2-one and (3Z)-4-(5-tert-butyl-2-hydroxyanilino)pent-3-en-2-one.

PubMed

Akerman, Kate J; Munro, Orde Q

2013-03-01

The Schiff base enaminones (3Z)-4-(5-ethylsulfonyl-2-hydroxyanilino)pent-3-en-2-one, C13H17NO4S, (I), and (3Z)-4-(5-tert-butyl-2-hydroxyanilino)pent-3-en-2-one, C15H21NO2, (II), were studied by X-ray crystallography and density functional theory (DFT). Although the keto tautomer of these compounds is dominant, the O=C-C=C-N bond lengths are consistent with some electron delocalization and partial enol character. Both (I) and (II) are nonplanar, with the amino-phenol group canted relative to the rest of the molecule; the twist about the N(enamine)-C(aryl) bond leads to dihedral angles of 40.5 (2) and -116.7 (1)° for (I) and (II), respectively. Compound (I) has a bifurcated intramolecular hydrogen bond between the N-H group and the flanking carbonyl and hydroxy O atoms, as well as an intermolecular hydrogen bond, leading to an infinite one-dimensional hydrogen-bonded chain. Compound (II) has one intramolecular hydrogen bond and one intermolecular C=O...H-O hydrogen bond, and consequently also forms a one-dimensional hydrogen-bonded chain. The DFT-calculated structures [in vacuo, B3LYP/6-311G(d,p) level] for the keto tautomers compare favourably with the X-ray crystal structures of (I) and (II), confirming the dominance of the keto tautomer. The simulations indicate that the keto tautomers are 20.55 and 18.86 kJ mol(-1) lower in energy than the enol tautomers for (I) and (II), respectively.

TOXICITY OF METHYL-TERT BYTYL ETHER (MTBE) TO PLANTS (AVENA SATIVA, ZEA MAYS, TRITICUM AESTIVUM, AND LACTUCA SATIVA)

EPA Science Inventory

Effects of Methyl tert-butyl ether (MTBE) on the germination of seeds and growth of the plant were studied in some laboratory experiments. Test plants were wild oat (Avena sative), sweet corn (Zea mays), wheat (Triticum aestivum), and lettuce (Lactuca sativa). Seed germination,...

IRIS Toxicological Review of Tert-Butyl Alcohol (Tert-Butanol) ...

EPA Pesticide Factsheets

EPA is developing an Integrated Risk Information System (IRIS) assessment of tert-butyl Alcohol (tert-butanol) and has released the public comment draft assessment for public comment and external peer review. When final, the assessment will appear on the IRIS database. This draft report is being released for public viewing and comment prior to a public meeting, providing an opportunity for the IRIS Program to engage in early discussions with stakeholders and the public on data that may be used to identify adverse health effects and characterize exposure-response relationships. EPA welcomes all comments on the draft literature search, preliminary evidence tables, and preliminary exposure-response arrays, such as remarks on the following: • the clarity and transparency of the materials; • the approach for identifying pertinent studies; • the selection of studies for data extraction to preliminary evidence tables and exposure-response arrays; • any methodological considerations that could affect the interpretation of or confidence in study results; and • any additional studies published or nearing publication that may provide data for the evaluation of human health hazard or dose-response relationships.

Shape-programmed nanofabrication: understanding the reactivity of dichalcogenide precursors.

PubMed

Guo, Yijun; Alvarado, Samuel R; Barclay, Joshua D; Vela, Javier

2013-04-23

Dialkyl and diaryl dichalcogenides are highly versatile and modular precursors for the synthesis of colloidal chalcogenide nanocrystals. We have used a series of commercially available dichalcogenide precursors to unveil the molecular basis for the outcome of nanocrystal preparations, more specifically, how precursor molecular structure and reactivity affect the final shape and size of II-VI semiconductor nanocrystals. Dichalcogenide precursors used were diallyl, dibenzyl, di-tert-butyl, diisopropyl, diethyl, dimethyl, and diphenyl disulfides and diethyl, dimethyl, and diphenyl diselenides. We find that the presence of two distinctively reactive C-E and E-E bonds makes the chemistry of these precursors much richer and interesting than that of other conventional precursors such as the more common phosphine chalcogenides. Computational studies (DFT) reveal that the dissociation energy of carbon-chalcogen (C-E) bonds in dichalcogenide precursors (R-E-E-R, E=S or Se) increases in the order (R): diallyl

Microfluidic White Organic Light-Emitting Diode Based on Integrated Patterns of Greenish-Blue and Yellow Solvent-Free Liquid Emitters

NASA Astrophysics Data System (ADS)

Kobayashi, Naofumi; Kasahara, Takashi; Edura, Tomohiko; Oshima, Juro; Ishimatsu, Ryoichi; Tsuwaki, Miho; Imato, Toshihiko; Shoji, Shuichi; Mizuno, Jun

2015-10-01

We demonstrated a novel microfluidic white organic light-emitting diode (microfluidic WOLED) based on integrated sub-100-μm-wide microchannels. Single-μm-thick SU-8-based microchannels, which were sandwiched between indium tin oxide (ITO) anode and cathode pairs, were fabricated by photolithography and heterogeneous bonding technologies. 1-Pyrenebutyric acid 2-ethylhexyl ester (PLQ) was used as a solvent-free greenish-blue liquid emitter, while 2,8-di-tert-butyl-5,11-bis(4-tert-butylphenyl)-6,12-diphenyltetracene (TBRb)-doped PLQ was applied as a yellow liquid emitter. In order to form the liquid white light-emitting layer, the greenish-blue and yellow liquid emitters were alternately injected into the integrated microchannels. The fabricated electro-microfluidic device successfully exhibited white electroluminescence (EL) emission via simultaneous greenish-blue and yellow emissions under an applied voltage of 100 V. A white emission with Commission Internationale de l’Declairage (CIE) color coordinates of (0.40, 0.42) was also obtained; the emission corresponds to warm-white light. The proposed device has potential applications in subpixels of liquid-based microdisplays and for lighting.

Simple and fast PO-CL method for the evaluation of antioxidant capacity of hydrophilic and hydrophobic antioxidants.

PubMed

Zargoosh, Kiomars; Ghayeb, Yousef; Azmoon, Behnaz; Qandalee, Mohammad

2013-08-01

A simple and fast procedure is described for evaluating the antioxidant activity of hydrophilic and hydrophobic compounds by using the peroxyoxalate-chemiluminescence (PO-CL) reaction of Bis(2,4,6-trichlorophenyl) oxalate (TCPO) with hydrogen peroxide in the presence of di(tert-butyl)2-(tert-butylamino)-5-[(E)-2-phenyl-1-ethenyl]3,4-furandicarboxylate as a highly fluorescent fluorophore. The IC50 values of the well-known antioxidants were calculated and the results were expressed as gallic equivalent antioxidant capacity (GEAC). It was found that the proposed method is free of physical quenching and oxidant interference, for this reason, proposed method is able to determine the accurate scavenging activity of the antioxidants to the free radicals. Finally, the proposed method was applied to the evaluation of antioxidant activity of complex real samples such as soybean oil and sunflower oil (as hydrophobic samples) and honey (as hydrophilic sample). To the best of our knowledge, this is the first time that total antioxidant activity can be determined directly in soybean oil, sunflower oil and honey (not in their extracts) using PO-CL reactions. Copyright © 2013 Elsevier B.V. All rights reserved.

New Molecular Design Concurrently Providing Superior Pure Blue, Thermally Activated Delayed Fluorescence and Optical Out-Coupling Efficiencies.

PubMed

Rajamalli, P; Senthilkumar, N; Huang, P-Y; Ren-Wu, C-C; Lin, H-W; Cheng, C-H

2017-08-16

Simultaneous enhancement of out-coupling efficiency, internal quantum efficiency, and color purity in thermally activated delayed fluorescence (TADF) emitters is highly desired for the practical application of these materials. We designed and synthesized two isomeric TADF emitters, 2DPyM-mDTC and 3DPyM-pDTC, based on di(pyridinyl)methanone (DPyM) cores as the new electron-accepting units and di(tert-butyl)carbazole (DTC) as the electron-donating units. 3DPyM-pDTC, which is structurally nearly planar with a very small ΔE ST , shows higher color purity, horizontal ratio, and quantum yield than 2DPyM-mDTC, which has a more flexible structure. An electroluminescence device based on 3DPyM-pDTC as the dopant emitter can reach an extremely high external quantum efficiency of 31.9% with a pure blue emission. This work also demonstrates a way to design materials with a high portion of horizontal molecular orientation to realize a highly efficient pure-blue device based on TADF emitters.

URINARY AND AMNIOTIC FLUID LEVELS OF PHTHALATE MONOESTERS IN RATS AFTER THE ORAL ADMINISTRATION OF DI(2-ETHYLHEXYL) PHTHALATE AND DI-N-BUTYL PHTHALATE

EPA Science Inventory

Two studies were designed to examine amniotic fluid and maternal urine concentrations of the di(2-ethylhexyl) phthalate (DEHP) metabolite mono(2-ethylhexyl) phthalate (MEHP) and the di-n-butyl phthalate (DBP) metabolite monobutyl phthalate (MBP) after administration of DEHP and D...

Difunctionalization of alkenes with iodine and tert-butyl hydroperoxide (TBHP) at room temperature for the synthesis of 1-(tert-butylperoxy)-2-iodoethanes.

PubMed

Wang, Hao; Chen, Cui; Liu, Weibing; Zhu, Zhibo

2017-01-01

We developed a direct vicinal difunctionalization of alkenes with iodine and TBHP at room temperature. This iodination and peroxidation in a one-pot synthesis produces 1-( tert -butylperoxy)-2-iodoethanes, which are inaccessible through conventional synthetic methods. This method generates multiple radical intermediates in situ and has excellent regioselectivity, a broad substrate scope and mild conditions. The iodine and peroxide groups of 1-( tert -butylperoxy)-2-iodoethanes have several potential applications and allow further chemical modifications, enabling the preparation of synthetically valuable molecules.

Electronic structure and reactivity of high-spin iron--alkyl- and--pterinperoxo complexes.

PubMed

Lehnert, Nicolai; Fujisawa, Kiyoshi; Solomon, Edward I

2003-01-27

The spectroscopic properties and electronic structure of the four-coordinate high-spin [FeIII(L3)(OOtBu)]+ complex (1; L3 = hydrotris(3-tert-butyl-5-isopropyl-1-pyrazolyl)borate; tBu = tert-butyl) are investigated and compared to the six-coordinated high-spin [Fe(6-Me3TPA)(OHx)(OOtBu)]x+ system (TPA = tris(2-pyridylmethyl)amine, x = 1 or 2) studied earlier [Lehnert, N.; Ho, R. Y. N.; Que, L., Jr.; Solomon, E. I. J. Am. Chem. Soc. 2001, 123, 12802-12816]. Complex 1 is characterized by Raman features at 889 and 830 cm-1 which are assigned to the O-O stretch (mixed with the symmetric C-C stretch) and a band at 625 cm-1 that corresponds to nu(Fe-O). The UV-vis spectrum shows a charge-transfer (CT) transition at 510 nm from the alkylperoxo pi v* (v = vertical to C-O-O plane) to a d orbital of Fe(III). A second CT is identified from MCD at 370 nm that is assigned to a transition from pi h* (h = horizontal to C-O-O plane) to an Fe(III) d orbital. For the TPA complex the pi v* CT is at 560 nm while the pi h* CT is to higher energy than 250 nm. These spectroscopic differences between four- and six-coordinate Fe(III)-OOR complexes are interpreted on the basis of their different ligand fields. In addition, the electronic structure of Fe-OOPtn complexes with the biologically relevant pterinperoxo ligand are investigated. Substitution of the tert-butyl group in 1 by pterin leads to the corresponding Fe(III)-OOPtn species (2), which shows a stronger electron donation from the peroxide to Fe(III) than 1. This is related to the lower ionization potential of pterin. Reduction of 2 by one electron leads to the Fe(II)-OOPtn complex (3), which is relevant as a model for potential intermediates in pterin-dependent hydroxylases. However, in the four-coordinate ligand field of 3, the additional electron is located in a nonbonding d orbital of iron. Hence, the pterinperoxo ligand is not activated for heterolytic cleavage of the O-O bond in this system. This is also evident from the calculated reaction energies that are endothermic by at least 20 kcal/mol.

A COMPARISON OF LIQUID AND GAS-PHASE PHOTOOXIDATION TREATMENT OF METHYL TERTIARY BUTYL ETHER: SYNTHETIC AND FIELD SAMPLES

EPA Science Inventory

The feasibility of photo-oxidation treatment of metyl tert-butyl either (MTBE) in water was investigated using two systems, 1) a slurry falling film photo-reactor, and 2) an integrated air-stripping with gas phase photooxidation system. MTBE-contaminated synthetic water and field...

Synthesis, spectroscopy, magnetic and redox behaviors of copper(II) complexes with tert-butylated salen type ligands bearing bis(4-aminophenyl)ethane and bis(4-aminophenyl)amide backbones.

PubMed

Kasumov, Veli T; Yerli, Yusuf; Kutluay, Aysegul; Aslanoglu, Mehmet

2013-03-01

New salen type ligands, N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-ethylenedianiline [(X=H (1), 5-tert-butyl (2)] and N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-amidedianiline [X=H (3), 5-tert (4)] and their copper(II) complexes 5-8, have been synthesized. Their spectroscopic (IR, (1)H NMR, UV/vis, ESR) properties, as well as magnetic and redox-reactivity behavior are reported. IR spectra of 7 and 8 indicate the coordination of amide oxygen atoms of 3 and 4 ligands to Cu(II). The solid state ESR spectra of 5-8 exhibits less informative exchange narrowed isotropic or anisotropic signals with weak unresolved low field patterns. The magnetic moments of 5 (2.92 μ(B) per Cu(II)) and 6 (2.79 μ(B) per Cu(II)) are unusual for copper(II) complexes and considerably higher than those for complexes 7 and 8. Cryogenic measurements (300-10 K) show weak antiferromagnetic exchange interactions between the copper(II) centers in complexes 6 and 8. The results of electrochemical and chemical redox-reactivity studies are discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

Chemical stabilization of polymers: Implications for dermal exposure to additives.

PubMed

Bartsch, N; Girard, M; Schneider, L; Weijgert, V Van De; Wilde, A; Kappenstein, O; Vieth, B; Hutzler, C; Luch, A

2018-04-16

Technical benefits of additives in polymers stand in marked contrast to their associated health risks. Here, a multi-analyte method based on gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) was developed to quantify polymer additives in complex matrices such as low-density polyethylene (LDPE) and isolated human skin layers after dermal exposure ex vivo. That way both technical aspects and dermal exposure were investigated. The effects of polymer additivation on the material were studied using the example of LDPE. To this end, a tailor-made polymer was applied in aging studies that had been furnished with two different mixtures of phenol- and diarylamine-based antioxidants, plasticizers and processing aids. Upon accelerated thermo-oxidative aging of the material, the formation of LDPE degradation products was monitored with attenuated total reflectance-Fourier transformed infrared (ATR-FTIR) spectroscopy. Compared to pure LDPE, a protective effect of added antioxidants could be observed on the integrity of the polymer. Further, thermo-oxidative degradation of the additives and its kinetics were investigated using LDPE or squalane as matrix. The half-lives of additives in both matrices revealed significant differences between the tested additives as well as between LDPE and squalane. For instance, 2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol (Antioxidant 2246) showed a half-life 12 times lower when incorporated in LDPE as compared to squalane. As a model for dermal exposure of consumers, human skin was brought into contact with the tailor-made LDPE containing additives ex vivo in static Franz diffusion cells. The skin was then analyzed for additives and decomposition products. This study proved 10 polymer additives of diverse pysicochemical properties and functionalities to migrate out of the polymer and eventually overcome the intact human skin barrier during contact. Moreover, their individual distribution within distinct skin layers was demonstrated. This is exemplified by the penetration of the procarcinogenic antioxidant N-phenylnaphthalen-2-amine (Neozon D) into the viable epidermis and the permeation through the skin of the neurotoxic plasticizer N-butylbenzenesulfonamide (NBBS). In addition, the analyses of additive degradation products in the isolated skin layers revealed the presence of 2-tert-butyl-4-methylphenol in all layers after contact to a polymer with substances of origin like Antioxidant 2246. Thus, attention needs to be paid to absorption of polymer additives together with their degradation products when it comes to dermal exposure assessment.

Effect of EMA and antioxidants on properties of thermoplastic starch blown films

NASA Astrophysics Data System (ADS)

Threepopnatkul, P.; Kulsetthanchalee, C.; Sittattrakul, A.; Kaewjinda, E.

2015-07-01

The objectives of this study were to investigate the effect of poly(ethylene-co-methyl acrylate) (EMA) at 10, 30 and 50 wt% on the morphological properties, moisture sorption, water vapor permeability and biodegradability of thermoplastic starch (TPS). Urea and formamide were used as a mixed plasticizer. In addition, the effect of antioxidants namely, 3,5-di-tert-butyl-4-hydroxyhydrocinnamate (DTBH), butylated hydroxytoluene (BHT) and bis(octadecyl)hydroxylamine (BOH) at 1 wt% on the properties of TPS/EMA film was investigated. TPS/EMA films were produced by a blown film molding machine and characterized by scanning electron microscropy, moisture sorption, water vapor permeability and biodegradability measurement. Results found that the increment of EMA content in the TPS matrix could improve the water sorption, water vapor permeability and biodegradability properties of TPS/EMA films. For biodegradation, the weight loss of the blended films was directly proportional to TPS content. Regarding the antioxidants effect, the water vapor permeability of TPS/EMA films containing DTBH was higher than the one with BOH and BHT. However, the antioxidants contributed little to the biodegradability of TPS/EMA films and had no effect on the moisture sorption of TPS/EMA films.

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

Wei, Xiaoliang; Xu, Wu; Huang, Jinhua

Nonaqueous redox flow batteries hold the promise to achieve higher energy density ascribed to the broader voltage window than their aqueous counterparts, but their current performance is limited by low redox material concentration, poor cell efficiency, and inferior cycling stability. We report a new nonaqueous total-organic flow battery based on high concentrations of 9-fluorenone as negative and 2,5-di-tert-butyl-1-methoxy-4-[2’-methoxyethoxy]benzene as positive redox materials. The supporting electrolytes are found to greatly affect the cycling stability of flow cells through varying chemical stabilities of the charged radical species, especially the 9-fluorenone radical anions, as confirmed by electron spin resonance. Such an electrolyte optimizationmore » sheds light on mechanistic understandings of capacity fading in flow batteries employing organic radical-based redox materials and demonstrates that rational design of supporting electrolyte is vital for stable cyclability.« less

Interplay of stereoelectronic and enviromental effects in tuning the structural and magnetic properties of a prototypical spin probe: further insights from a first principle dynamical approach.

PubMed

Pavone, Michele; Cimino, Paola; De Angelis, Filippo; Barone, Vincenzo

2006-04-05

The nitrogen isotropic hyperfine coupling constant (hcc) and the g tensor of a prototypical spin probe (di-tert-butyl nitroxide, DTBN) in aqueous solution have been investigated by means of an integrated computational approach including Car-Parrinello molecular dynamics and quantum mechanical calculations involving a discrete-continuum embedding. The quantitative agreement between computed and experimental parameters fully validates our integrated approach. Decoupling of the structural, dynamical, and environmental contributions acting onto the spectral observables allows an unbiased judgment of the role played by different effects in determining the overall experimental observables and highlights the importance of finite-temperature vibrational averaging. Together with their intrinsic interest, our results pave the route toward more reliable interpretations of EPR parameters of complex systems of biological and technological relevance.

Crystal structure of (2,4-di-tert-butyl-6-{[(6,6'-dimethyl-2'-oxido-1,1'-biphenyl-2-yl)imino]methyl}phenolato-κ(3) O,N,O')bis(propan-2-olato-κO)titanium(IV).

PubMed

Chen, Liang; Wang, Huiran; Deng, Xuebin

2014-09-01

In the mononuclear Ti(IV) title complex, [Ti(C29H33NO2)(C3H6O)2], the TiNO4 coordination polyhedron comprises an N-atom and two O-atom donors from the dianionic Schiff base ligand and two O-atom donors from monodentate isopropoxide anions. The stereochemistry is distorted trigonal-bipyramidal with the N-donor in an elongated axial site [Ti-N = 2.2540 (17) Å], the O-donors having normal Ti-O bond lengths [1.7937 (14) Å (axial)-1.8690 (14) Å]. In the crystal, C-H⋯π inter-actions link mol-ecules into centrosymmetric dimers.

Ground-State Distortion in N-Acyl-tert-butyl-carbamates (Boc) and N-Acyl-tosylamides (Ts): Twisted Amides of Relevance to Amide N-C Cross-Coupling.

PubMed

Szostak, Roman; Shi, Shicheng; Meng, Guangrong; Lalancette, Roger; Szostak, Michal

2016-09-02

Amide N-C(O) bonds are generally unreactive in cross-coupling reactions employing low-valent transition metals due to nN → π*C═O resonance. Herein we demonstrate that N-acyl-tert-butyl-carbamates (Boc) and N-acyl-tosylamides (Ts), two classes of acyclic amides that have recently enabled the development of elusive amide bond N-C cross-coupling reactions with organometallic reagents, are intrinsically twisted around the N-C(O) axis. The data have important implications for the design of new amide cross-coupling reactions with the N-C(O) amide bond cleavage as a key step.

Methyl tert-butyl ether biodegradation by microbial consortia obtained from soil samples of gasoline-polluted sites in Mexico.

PubMed

Morales, Marcia; Velázquez, Elia; Jan, Janet; Revah, Sergio; González, Uriel; Razo-Flores, Elías

2004-02-01

Microbial consortia obtained from soil samples of gasoline-polluted sites were individually enriched with pentane, hexane, isooctane and toluene. Cometabolism with methyl tert-butyl ether, (MTBE), gave maximum degradation rates of 49, 12, 32 and 0 mg g(-1)protein h(-1), respectively. MTBE was fully degraded even when pentane was completely depleted with a cometabolic coefficient of 1 mgMTBE mg(-1)pentane. The analysis of 16S rDNA from isolated microorganisms in the pentane-adapted consortia showed that microorganisms could be assigned to Pseudomonas. This is the first work reporting the cometabolic mineralization of MTBE by consortium of this genus.

Rotational Investigation of the Adducts of Formic Acid with Alcohols, Ethers and Esters

NASA Astrophysics Data System (ADS)

Evangelisti, Luca; Spada, Lorenzo; Li, Weixing; Caminati, Walther

2016-06-01

Mixtures of formic acid with methyl alcohol, with isopropyl alcohol, with tert-butyl alcohol, with dimethylether and with isopropylformiate have been supersonically expanded as pulsed jets. The obtained cool plumes have been analyzed by Fourier transform microwave spectroscopy. It has been possible to assign the rotational spectra of the 1:1 adducts of formic acid with tert-butyl alcohol, with dimethyl ether and with isopropylformiate. The conformational shapes and geometries of these adducts, as well as the topologies of their itermolecular hydrogen bonds will be presented. An explanation is given of the failure of the assignments of the rotational spectra of the adducts of formic acid with methyl alcohol and isopropyl alcohol.

Di-n-butyl Phthalate (DNBP) and Diisobutyl Phthalate (DiBP) Metabolism in a Human Volunteer after Single Oral Doses [Journal Article

EPA Science Inventory

An individual (male, 36 years, 87 kg) ingested two separate doses of di-n-butyl phthalate (DnBP) and diisobutyl phthalate (DiBP) at a rate of ~60 µg/kg. Key monoester and oxidized metabolites were identified and quantified in urine continuously collected until 48 hours post dos...

PREVENTION OF POLYURETHANE OXIDATIVE DEGRADATION WITH PHENOLIC-ANTIOXIDANTS COVALENTLY ATTACHED TO THE HARD SEGMENTS: STRUCTURE FUNCTION RELATIONSHIPS

PubMed Central

Stachelek, Stanley J; Alferiev, Ivan; Ueda, Masako; Eckels, Edward C.; Gleason, Kevin T.; Levy, Robert J

2010-01-01

Oxidative degradation of the polyurethane elastomeric (PU) components greatly reduces the efficacy of PU containing cardiovascular devices. Covalently appending the phenol-based antioxidant, 4-substituted 2,6-di-tert-butylphenol (DBP), to PU hard segments effectively reduced oxidative degradation of the PU in vivo and in vitro in prior studies by our group. In these experiments we analyze the contribution of the tethering molecule to the antioxidant capabilities of the DBP modified PU. Bromoalkylation chemistry was used to link DBP to the hard segment of the polyether polyurethane, Tecothane, via our original linker (PU-DBP), or variants containing side chains with 1 (PU-C-DBP) or 3 (PU-3C-DBP) carbons. Two additional DBP variants were fabricated in which the DBP group was appended to the alkyl chain via an oxygen atom (PU-O-DBP) or an amide linkage in the middle of the tether (PU-NHCO-DBP). All DBP variant films and unmodified control films were subject to oxidative degradation via 15 day immersion in a solution of 20% H2O2 + 0.1 M CoCl2. At the end of the oxidation protocol films were analyzed for the presence of oxidation related endpoints via scanning electron microscopy, contact angle measurements and Fourier transformation infrared spectroscopy (FTIR). All DBP containing variants resisted oxidation damage significantly better than the unmodified control PU. SEM analysis of oxidized PU-C-DBP and PU-O-DBP showed evidence of surface cracking consistent with oxidative degradation of the PU surfaces. Similarly there was a trend in increased ether cross-linking, a marker for oxidative degradation, in PU-C-DBP and PU-NHCO-DBP films. Consistent with these FTIR results, both PU-C-DBP and PU-NHCO-DBP had significant reductions in measured surface hydrophobicity as a result of oxidation. These data show for the first time that the choice of linker molecule significantly affects the efficiency of the linked phenolic antioxidant. PMID:20306526

Formation of Alkenes via Degradation of tert-Alkyl Ethers and Alcohols by Aquincola tertiaricarbonis L108 and Methylibium spp. ▿†

PubMed Central

Schäfer, Franziska; Muzica, Liudmila; Schuster, Judith; Treuter, Naemi; Rosell, Mònica; Harms, Hauke; Müller, Roland H.; Rohwerder, Thore

2011-01-01

Bacterial degradation pathways of fuel oxygenates such as methyl tert-butyl and tert-amyl methyl ether (MTBE and TAME, respectively) have already been studied in some detail. However, many of the involved enzymes are still unknown, and possible side reactions have not yet been considered. In Aquincola tertiaricarbonis L108, Methylibium petroleiphilum PM1, and Methylibium sp. strain R8, we have now detected volatile hydrocarbons as by-products of the degradation of the tert-alkyl ether metabolites tert-butyl and tert-amyl alcohol (TBA and TAA, respectively). The alkene isobutene was formed only during TBA catabolism, while the beta and gamma isomers of isoamylene were produced only during TAA conversion. Both tert-alkyl alcohol degradation and alkene production were strictly oxygen dependent. However, the relative contribution of the dehydration reaction to total alcohol conversion increased with decreasing oxygen concentrations. In resting-cell experiments where the headspace oxygen content was adjusted to less than 2%, more than 50% of the TAA was converted to isoamylene. Isobutene formation from TBA was about 20-fold lower, reaching up to 4% alcohol turnover at low oxygen concentrations. It is likely that the putative tert-alkyl alcohol monooxygenase MdpJ, belonging to the Rieske nonheme mononuclear iron enzymes and found in all three strains tested, or an associated enzymatic step catalyzed the unusual elimination reaction. This was also supported by the detection of mdpJK genes in MTBE-degrading and isobutene-emitting enrichment cultures obtained from two treatment ponds operating at Leuna, Germany. The possible use of alkene formation as an easy-to-measure indicator of aerobic fuel oxygenate biodegradation in contaminated aquifers is discussed. PMID:21742915

The “Gate Keeper” Role of Trp222 Determines the Enantiopreference of Diketoreductase toward 2-Chloro-1-Phenylethanone

PubMed Central

Lu, Zhuo; Liu, Nan; Chen, Yijun

2014-01-01

Trp222 of diketoreductase (DKR), an enzyme responsible for reducing a variety of ketones to chiral alcohols, is located at the hydrophobic dimeric interface of the C-terminus. Single substitutions at DKR Trp222 with either canonical (Val, Leu, Met, Phe and Tyr) or unnatural amino acids (UAAs) (4-cyano-L-phenylalanine, 4-methoxy-L-phenylalanine, 4-phenyl-L-phenyalanine, O-tert-butyl-L-tyrosine) inverts the enantiotope preference of the enzyme toward 2-chloro-1-phenylethanone with close side chain correlation. Analyses of enzyme activity, substrate affinity and ternary structure of the mutants revealed that substitution at Trp222 causes a notable change in the overall enzyme structure, and specifically in the entrance tunnel to the active center. The size of residue 222 in DKR is vital to its enantiotope preference. Trp222 serves as a “gate keeper” to control the direction of substrate entry into the active center. Consequently, opposite substrate-binding orientations produce respective alcohol enantiomers. PMID:25072248

Analysis of phthalic acid diesters, monoester, and other plasticizers in polyvinyl chloride household products in Japan.

PubMed

Kawakami, Tsuyoshi; Isama, Kazuo; Matsuoka, Atsuko

2011-01-01

The aim of this study was to determine the concentrations of six phthalic acid diesters (PAEs) [di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP), diisononyl phthalate (DINP), di-n-octyl phthalate (DNOP), and diisodecyl phthalate (DIDP)], two non-phthalic plasticizers [di(2-ethylhexyl) adipate (DEHA), 2,2,4-trimethyl-1,3-pentanediol diisobutylate (TMPDIB)], and mono 2-ethylhexyl phthalate(MEHP) in polyvinyl chloride (PVC) household products that children often places in their mouths and/or contact with their skin (41 products, 47 samples) in Japan. The detection frequencies of the studied compounds were as follows: DEHP (79 %), DINP-2 (13 %), DINP-1 (11 %), DBP (8.5 %), DEHA (8.5 %), DIDP (4.3 %), and DNOP (2.1 %). Concentrations of these compounds ranged from 0.021 % to 48 %. BBP and TMPDIB were not detected in the all samples. Most samples contained DEHP and DINP at high concentrations over 0.1 %. High concentrations of PAEs were detected in PVC household products that appear appealing to children and can possibly be licked and chewed by them. Di(2-ethylhexyl) terephtalete, diisononyl 1,2-cyclohexanedicarboxylic acid, acetyl tributyl citrate, and di(2-ethylhexyl) 4-cyclohexene-1,2-dicarboxylate used as substitute plasticizers were also detected in several samples. MEHP was present in 70 % of the samples, with concentrations ranging from trace amounts to 140 μg/g. The ratios of MEHP against DEHP were 6.2 × 10(-4) to 1.6 × 10(-1) %. MEHP in the household products investigated in this study was most probably an impurity in DEHP. The high concentrations of PAEs detected in products that children often place in their mouth reveal the importance of replacing plasticizers in common household products, and not just children's toys, with safer alternatives.

21 CFR 178.2550 - 4-Hydroxymethyl-2,6-di-tert-butylphenol.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true 4-Hydroxymethyl-2,6-di-tert-butylphenol. 178.2550 Section 178.2550 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: ADJUVANTS, PRODUCTION AIDS, AND...

21 CFR 178.2550 - 4-Hydroxymethyl-2,6-di-tert-butylphenol.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false 4-Hydroxymethyl-2,6-di-tert-butylphenol. 178.2550 Section 178.2550 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: ADJUVANTS, PRODUCTION AIDS, AND...

Directed Evolution of Carbonyl Reductase from Rhodosporidium toruloides and Its Application in Stereoselective Synthesis of tert-Butyl (3R,5S)-6-Chloro-3,5-dihydroxyhexanoate.

PubMed

Liu, Zhi-Qiang; Wu, Lin; Zhang, Xiao-Jian; Xue, Ya-Ping; Zheng, Yu-Guo

2017-05-10

tert-Butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate ((3R,5S)-CDHH) is a key intermediate of atorvastatin and rosuvastatin synthesis. Carbonyl reductase RtSCR9 from Rhodosporidium toruloides exhibited excellent activity toward tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH). For the activity of RtSCR9 to be improved, random mutagenesis and site-saturation mutagenesis were performed. Three positive mutants were obtained (mut-Gln95Asp, mut-Ile144Lys, and mut-Phe156Gln). These mutants exhibited 1.94-, 3.03-, and 1.61-fold and 1.93-, 3.15-, and 1.97-fold improvement in the specific activity and k cat /K m , respectively. Asymmetric reduction of (S)-CHOH by mut-Ile144Lys coupled with glucose dehydrogenase was conducted. The yield and enantiomeric excess of (3R,5S)-CDHH reached 98 and 99%, respectively, after 8 h bioconversion in a single batch reaction with 1 M (S)-CHOH, and the space-time yield reached 542.83 mmol L -1 h -1 g -1 wet cell weight. This study presents a new carbonyl reductase for efficient synthesis of (3R,5S)-CDHH.

Studies on the Conformational Landscape of Tert-Butyl Acetate Using Microwave Spectroscopy and Quantum Chemical Calculations

NASA Astrophysics Data System (ADS)

Zhao, YueYue; Mouhib, Halima; Li, Guohua; Stahl, Wolfgang; Kleiner, Isabelle

2014-06-01

The tert-Butyl acetate molecule was studied using a combination of quantum chemical calculations and molecular beam Fourier transform microwave spectroscopy in the 9 to 14 GHz range. Due to its rather rigid frame, the molecule possesses only two different conformers: one of Cs and one of C1 symmetry. According to ab initio calculations, the Cs conformer is 46 kJ/mol lower in energy and is the one observed in the supersonic jet. We report on the structure and dynamics of the most abundant conformer of tert-butyl acetate, with accurate rotational and centrifugal distortion constants. Additionally, the barrier to internal rotation of the acetyl methyl group was determined. Splittings due to the internal rotation of the methyl group of up to 1.3 GHz were observed in the spectrum. Using the programs XIAM and BELGI-Cs, we determine the barrier height to be about 113 cm-1 and compare the molecular parameters obtained from these two codes. Additionally, the experimental rotational constants were used to validate numerous quantum chemical calculations. This study is part of a larger project which aims at determining the lowest energy conformers of organic esters and ketones which are of interest for flavor or perfume synthetic applications Project partly supported by the PHC PROCOPE 25059YB.

Redox Active Transition Metal ions Make Melanin Susceptible to Chemical Degradation Induced by Organic Peroxide.

PubMed

Zadlo, Andrzej; Pilat, Anna; Sarna, Michal; Pawlak, Anna; Sarna, Tadeusz

2017-12-01

With aging, retinal pigment epithelium melanosomes, by fusion with the age pigment lipofuscin, form complex granules called melanolipofuscin. Lipofuscin granules may contain oxidized proteins and lipid hydroperoxides, which in melanolipofuscin could chemically modify melanin polymer, while transition metal ions present in melanin can accelerate such oxidative modifications. The aim of this research was to examine the effect of selected transition metal ions on melanin susceptibility to chemical modification induced by the water-soluble tert-butyl hydroperoxide used as an oxidizing agent. Synthetic melanin obtained by DOPA autooxidation and melanosomes isolated from bovine retinal pigment epithelium were analyzed. To monitor tert-butyl hydroperoxide-induced oxidative changes of DMa and BMs, electron paramagnetic resonance spectroscopy, UV-vis absorption spectroscopy, dynamic light scattering, atomic force microscopy and electron paramagnetic resonance oximetry were employed. These measurements revealed that both copper and iron ions accelerated chemical degradation induced by tert-butyl hydroperoxide, while zinc ions had no effect. Strong prooxidant action was detected only in the case of melanosomes and melanin degraded in the presence of iron. It can be postulated that similar chemical processes, if they occur in situ in melanolipofuscin granules of the human retinal pigment epithelium, would modify antioxidant properties of melanin and its reactivity.

Effect of 3-(3'-tert-butyl-4'-hydroxyphenyl)propyl thiosulfonate sodium on expression of GSTP1 and NQO1 genes and protein transcription factors in BALB/c mouse liver.

PubMed

Shintyapina, A B; Safronova, O G; Vavilin, V A; Kandalintseva, N V; Prosenko, A E; Lyakhovich, V V

2014-08-01

The study examined dynamics of the effect of novel phenol antioxidant preparation 3-(3'-tertbutyl- 4'-hydroxyphenyl)propyl thiosulfonate sodium (TS-13) on expression of antioxidant protection enzymes genes GSTP1 and NQO1 and on the content of protein transcription factors NF-κB and ATF-2 in mouse liver. Expression of GSTP1 gene decreased significantly on days 4 and 7 after per os administration of TS-13 (100 mg/kg), but increased on post-administration day 14. On days 7 and 14 post-administration, expression of NQO1 gene was significantly increased. On day 7, the hepatic content of the phosphorylated form of ATF-2 and two subunits of nuclear factor NF-κB (p50, p65) decreased significantly.

Effect of benzene, toluene, ethylbenzene, and p-xylene (BTEX) mixture on biodegradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) by pure culture UC1.

PubMed

Pruden, Amy; Suidan, Makram

2004-08-01

The effect of a BTEX mixture on the biodegradation of methyl tert-butyl ether (MTBE) and its degradation intermediate, tert-butyl alcohol (TBA) was investigated in the pure bacterial culture UC1, which has been identified to be a strain of the known MTBE-degrader PM1 based on greater than 99% 16S rDNA similarity. Several degradation studies were carried out on UC1 at three initial concentration levels of MTBE or TBA: 6-7; 15-17; and 40-45 mg/l, both with and without BTEX present cumulatively at about half of the MTBE or TBA molar mass in the system. The BTEX mixture was observed not to affect either the rate or the degradation lag period of MTBE or TBA degradation, except that the TBA degradation rate actually increased when BTEX was present initially in the highest concentration studies. When serving as the sole substrate, the MTBE degradation rate ranged from 48 +/- 1.2 to 200 +/- 7.0 mg(MTBE)/g(dw) h, and the TBA degradation rate from 140 +/- 18 to 530 +/- 70 mg(TBA)/g(dw) h. When present with BTEX, MTBE and TBA rates ranged from 46 +/- 2.2 to 210 +/- 14 and 170 +/- 28 to 780 +/- 43 mg(TBA)/g(dw) h, respectively. In studies where varying concentrations of TBA were present with 5 mg/l MTBE, both compounds were degraded simultaneously with no obvious preference for either substrate. In the highest concentration study of TBA with 5 mg/l MTBE, BTEX was also observed to increase the ultimate rate of TBA degradation. In addition to exploring the affect of BTEX, this study also provides general insight into the metabolism of MTBE and TBA by pure culture UC1.

A siloxane-incorporated copolymer as an in situ cross-linkable binder for high performance silicon anodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Jeena, M. T.; Bok, Taesoo; Kim, Si Hoon; Park, Sooham; Kim, Ju-Young; Park, Soojin; Ryu, Ja-Hyoung

2016-04-01

The electrochemical performance of Li-ion batteries (LIBs) can be highly tuned by various factors including the morphology of the anode material, the nature of the electrolyte, the binding material, and the percentage of conducting materials. Binding materials have been of particular interest to researchers over the decades as a means to further improve the cycle durability and columbic efficiency of LIBs. Such approaches include the introduction of different polymeric binders such as poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), and alginic acid (Alg) into the Si anode of LIBs. To achieve a better efficiency of LIBs, herein, we introduce a novel copolymer, poly(tert-butyl acrylate-co-triethoxyvinylsilane) (TBA-TEVS), as an efficient binder with stable cycle retention and excellent specific capacity. The binder forms a highly interconnected three-dimensional network upon thermal treatment as a result of de-protection of the tert-butyl group and the consequent inter-intra condensation reaction, which minimizes pulverization of the Si nanoparticles. Moreover, the siloxane group is expected to promote the formation of stable solid-electrolyte-interface (SEI) layers. A series of random copolymers were synthesized by varying the molar ratio of tert-butyl acrylate and triethoxyvinylsilane. Twenty-one percent of TEVS in the TBS-TEVS copolymer gave rise to a superior performance as a binder for Si anodes, where the anodes showed a stable specific capacity of 2551 mA h g-1 over hundreds of cycles and an initial columbic efficiency (ICE) of 81.8%.The electrochemical performance of Li-ion batteries (LIBs) can be highly tuned by various factors including the morphology of the anode material, the nature of the electrolyte, the binding material, and the percentage of conducting materials. Binding materials have been of particular interest to researchers over the decades as a means to further improve the cycle durability and columbic efficiency of LIBs. Such approaches include the introduction of different polymeric binders such as poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), and alginic acid (Alg) into the Si anode of LIBs. To achieve a better efficiency of LIBs, herein, we introduce a novel copolymer, poly(tert-butyl acrylate-co-triethoxyvinylsilane) (TBA-TEVS), as an efficient binder with stable cycle retention and excellent specific capacity. The binder forms a highly interconnected three-dimensional network upon thermal treatment as a result of de-protection of the tert-butyl group and the consequent inter-intra condensation reaction, which minimizes pulverization of the Si nanoparticles. Moreover, the siloxane group is expected to promote the formation of stable solid-electrolyte-interface (SEI) layers. A series of random copolymers were synthesized by varying the molar ratio of tert-butyl acrylate and triethoxyvinylsilane. Twenty-one percent of TEVS in the TBS-TEVS copolymer gave rise to a superior performance as a binder for Si anodes, where the anodes showed a stable specific capacity of 2551 mA h g-1 over hundreds of cycles and an initial columbic efficiency (ICE) of 81.8%. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01559j

Draft genome sequence of Methylibium sp. strain T29, a novel fuel oxygenate-degrading bacterial isolate from Hungary.

PubMed

Szabó, Zsolt; Gyula, Péter; Robotka, Hermina; Bató, Emese; Gálik, Bence; Pach, Péter; Pekker, Péter; Papp, Ildikó; Bihari, Zoltán

2015-01-01

Methylibium sp. strain T29 was isolated from a gasoline-contaminated aquifer and proved to have excellent capabilities in degrading some common fuel oxygenates like methyl tert-butyl ether, tert-amyl methyl ether and tert-butyl alcohol along with other organic compounds. Here, we report the draft genome sequence of M. sp. strain T29 together with the description of the genome properties and its annotation. The draft genome consists of 608 contigs with a total size of 4,449,424 bp and an average coverage of 150×. The genome exhibits an average G + C content of 68.7 %, and contains 4754 protein coding and 52 RNA genes, including 48 tRNA genes. 71 % of the protein coding genes could be assigned to COG (Clusters of Orthologous Groups) categories. A formerly unknown circular plasmid designated as pT29A was isolated and sequenced separately and found to be 86,856 bp long.

Absolute rate constants of alkoxyl radical reactions in aqueous solution. [Tert-butyl hydroperoxide

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

Erben-Russ, M.; Michel, C.; Bors, W.

1987-04-23

The pulse radiolysis technique was used to generate the alkoxyl radical derived from tert-butyl hydroperoxide (/sup t/BuOOH) in aqueous solution. The reactions of this radical with 2,2'-azinobis(3-ethyl-6-benzothiazolinesulfonate) (ABTS) and promethazine were monitored by kinetic spectroscopy. The unimolecular decay rate constant of the tert-butoxyl radical (/sup t/BuO) was determined to be 1.4 x 10/sup 6/ s/sup -1/. On the basis of this value, the rate constants for /sup t/BuO attack on quercetin, crocin, crocetin, ascorbate, isoascorbate, trolox c, glutathione, thymidine, adenosine, guanosine, and unsaturated fatty acids were determined. In addition, the reaction of /sup t/BuO with the polyunsaturated fatty acids (PUFA)more » was observed by directly monitoring the formation of the fatty acid pentadienyl radicals. Interestingly, the attack of /sup t/BuO on PUFA was found to be faster by about one order of magnitude as compared to the same reaction in a nonpolar solvent.« less

Toxicokinetics of ethers used as fuel oxygenates.

PubMed

Dekant, W; Bernauer, U; Rosner, E; Amberg, A

2001-10-15

The toxicokinetics and biotransformation of methyl-tert.butyl ether (MTBE), ethyl-tert.butyl ether (ETBE) and tert.amyl-methyl ether (TAME) in rats and humans are summarized. These ethers are used as gasoline additives in large amounts, and thus, a considerable potential for human exposure exists. After inhalation exposure MTBE, ETBE and TAME are rapidly taken up by both rats and humans; after termination of exposure, clearance by exhalation and biotransformation to urinary metabolites is rapid in rats. In humans, clearance by exhalation is slower in comparison to rats. Biotransformation of MTBE and ETBE is both qualitatively and quantitatively similar in humans and rats after inhalation exposure under identical conditions. The extent of biotransformation of TAME is also quantitatively similar in rats and humans; the metabolic pathways, however, are different. The results suggest that reactive and potentially toxic metabolites are not formed during biotransformation of these ethers and that toxic effects of these compounds initiated by covalent binding to cellular macromolecules are unlikely.

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

Zhang, W.; Chang, Q.G.; Liu, W.D.

A series of follow-up investigations were performed to produce data for improving the four-indicator carbon selection method that we developed to identify high-potential activated carbons effective for removing specific organic water pollutants. The carbon's pore structure and surface chemistry are dependent on the raw material and the activation process. Coconut carbons have relatively more small pores than large pores; coal and apricot nutshell/walnut shell fruit carbons have the desirable pore structures for removing adsorbates of all sizes. Chemical activation, excessive activation, and/or thermal reactivation enlarge small pores, resulting in reduced phenol number and higher tannic acid number. Activated carbon's phenol,more » iodine, methylene blue, and tannic acid numbers are convenient indicators of its surface area and pore volume of pore diameters < 10, 10-15, 15-28, and > 28 angstrom, respectively. The phenol number of a carbon is also a good indicator of its surface acidity of oxygen-containing organic functional groups that affect the adsorptive capacity for aromatic and other small polar organics. The tannic acid number is an indicator of carbon's capacity for large, high-molecular-weight natural organic precursors of disinfection by-products in water treatment. The experimental results for removing nitrobenzene, methyl-tert-butyl ether, 4,4-bisphenol, humic acid, and the organic constituents of a biologically treated coking-plant effluent have demonstrated the effectiveness of this capacity-indicator-based method of carbon selection.« less

Fragmentation characteristics of hydroxycinnamic acids in ESI-MSn by density functional theory.

PubMed

Yin, Zhi-Hui; Sun, Chang-Hai; Fang, Hong-Zhuang

2017-07-01

This work aims to analyze the electrospray ionization multistage mass spectrometry (ESI-MS n ) fragmentation characteristics of hydroxycinnamic acids (HCAs) in negative ion mode. The geometric parameters, energies, natural bond orbitals and frontier orbitals of fragments were calculated by density functional theory (DFT) to investigate mass spectral fragmentation mechanisms. The results showed that proton transfer always occurred during fragmentation of HCAs; their quasi-molecular ions ([M - H] - ) existed in more than one form and were mainly with the lowest energy. The fragmentation characteristics included the followings: (1) according to the different substitution position of phenolic hydroxyl group, the ring contraction reaction by CO elimination from benzene was in an increasingly difficult order: m-phenolic hydroxyl > p-phenolic hydroxyl > o-phenolic hydroxyl; and (2) ortho effect always occurred in o-dihydroxycinnamic acids (o-diHCAs), i.e. one phenolic hydroxyl group offered H + , which combined with the other one to lose H 2 O. In addition, there was a nucleophilic reaction during ring contraction in diHCAs that oxygen atom attacked the carbon atom binding with the other phenolic hydroxyl to lose CO 2 . The fragmentation characteristics and mechanism of HCAs could be used for analysis and identification of such compounds quickly and effectively, and as reference for structural analogues by ESI-MS. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

A calix[4]arene derivative and its selective interaction with drugs (clofibric acid, diclofenac and aspirin).

PubMed

Danil de Namor, Angela F; Al Nuaim, Maan; Villanueva Salas, Jose A; Bryant, Sophie; Howlin, Brendan

2017-03-30

The synthesis and characterisation of a partially substituted calix[4]arene, namely, 5,11,17,23-tetra-tert-butyl,25,27-bis[aminoethoxy] 26,28-dihydroxycalix[4]arene are reported. Its interaction with commonly used pharmaceuticals (clofibric acid, diclofenac and aspirin) was investigated by spectroscopic ( 1 H NMR and UV), electrochemical (conductance measurements) and thermal (titration calorimetry) techniques. It is concluded on the basis of the experimental work and molecular simulation studies that the receptor interacts selectively with these drugs. Preliminary studies on the selective extraction of these pharmaceuticals from water by the calix receptor are reported and the potential for a carrier mediated sensor based on this ligand for 'on site' monitoring of pharmaceuticals is discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

t-Butyl-Oxycarbonylated Diamines as Building Blocks for Isocyanate-Free Polyurethane/Urea Dispersions and Coatings.

PubMed

Ma, Shuang; Zhang, Huiyi; Sablong, Rafaël J; Koning, Cor E; van Benthem, Rolf A T M

2018-05-01

t-Butyl-oxycarbonylated diamines ("di-Boc-carbamates") are investigated as dicarbamate monomers for diamine/dicarbamate polymerizations. Polyureas (PUs) and polyurethanes (PURs) with high molecular weights are prepared from stoichiometric polymerizations of diamines or diols with N-N'-di-t-butyl-oxycarbonyl isophorone diamine (DiBoc-IPDC) using KOt-Bu as a catalyst, while gelation is observed when an excess of DiBoc-IPDC is used with respect to the diamines or diols. Stable dispersions are obtained from PUs and PURs with 3,3'-diamino-N-methyldipropylamine (DMDPA) as internal dispersing agent. The corresponding PU-based coatings exhibit superior mechanical properties and solvent resistances compared to the polyurethane urea coatings synthesized from diols, DiBoc-IPDC, and DMDPA. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flash Pyrolysis of t-Butyl Hydroperoxide and Di-t-butyl Peroxide: Evidence of Roaming in the Decomposition of Organic Hydroperoxides.

PubMed

Jones, Paul J; Riser, Blake; Zhang, Jingsong

2017-10-19

Thermal decomposition of t-butyl hydroperoxide and di-t-butyl peroxide was investigated using flash pyrolysis (in a short reaction time of <100 μs) and vacuum-ultraviolet (λ = 118.2 nm) single-photon ionization time-of-flight mass spectrometry (VUV-SPI-TOFMS) at temperatures up to 1120 K and quantum computational methods. Acetone and methyl radical were detected as the predominant products in the initial decomposition of di-t-butyl peroxide via O-O bond fission. In the initial dissociation of t-butyl hydroperoxide, acetone, methyl radical, isobutylene, and isobutylene oxide products were identified. The novel detection of the unimolecular formation of isobutylene oxide, as supported by the computational study, was found to proceed via a roaming hydroxyl radical facilitated by a hydrogen-bonded intermediate. This new pathway could provide a new class of reactions to consider in the modeling of the low temperature oxidation of alkanes.

a Computational Tddft Study on Intramolecular Charge Transfer in Di-Tert and 2,4,6-TRICYANOANILINES.

NASA Astrophysics Data System (ADS)

Fujiwara, Takashige; Zgierski, Marek Z.

2014-06-01

We have carried out TDDFT computational studies on the low-lying excited states of di-tert-butylaminobenzonitrile and 2,4,6-tricyanoaniline compounds that exhibit unusual photophysical behaviors associated with the intramolecular charge transfer (ICT). For both 3- and 4-di-tert-butylamino)benzonitriles (m-DTBABN and p-DTBABN, respectively) show the ICT formation, and p-DTBABN appears to be the only meta-substituted aminobenzonitrile that exhibits the ICT formation. The TDDFT calculations indicate evidence that the ultrafast ICT formation in p-DTBABN and m-DTBABN is due to the sequential state switches: ππ*(La)→ πσ*→ ICT in the presence of conical intersections among the three closely-lying excited-states. On the other hand, 2,4,6-tricyanoaniline does not show clear evidence for the LE (locally excited) state → ICT state formation from steady-state fluorescence studies, despite the greater electron acceptor strength of tricycanobenzene as compared to monocyanobenzene, which is part of a 4-(dimethylamino)benzonitrile (p-DMABN) compound. However, it is predicted that 2,4,6-tricyano-N,N-dimethylaniline (TCDMA), but not 2,4,6-tricyanoaniline (TCA), possesses two ICT states, which show the ICT-characterized quinoidal structures and lie below the initially photo-excited S1(ππ*) state. The CC2 calculations further predict two conformers as labeled with quinoidal (ICT--Q) and anti-quinoidal (ICT--AQ) structures are rapidly interconnecting with each other. The lower energy ICT--Q structure tends to be populated from the unstable ICT--AQ structure, which is responsible for the observed time-resolved fluorescence as well as the excited-state absorption from the mixed S1(ππ*)/ICT state of TCDMA. In both cases for TCDMA and TCA, the πσ* state locates significantly higher in energy than the S1(ππ*) state (and the ICT state for TCA), thus precluding the πσ*→ ICT formation, which is believed to occur in a p-DMABN in polar environments.

U.S. Geological Survey laboratory method for methyl tert-Butyl ether and other fuel oxygenates

USGS Publications Warehouse

Raese, Jon W.; Rose, Donna L.; Sandstrom, Mark W.

1995-01-01

Methyl tert-butyl ether (MTBE) was found in shallow ground-water samples in a study of 8 urban and 20 agricultural areas throughout the United States in 1993 and 1994 (Squillace and others, 1995, p. 1). The compound is added to gasoline either seasonally or year round in many parts of the United States to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL), near Denver, uses state-of-the-art technology to analyze samples for MTBE as part of the USGS water-quality studies. In addition, the NWQL offers custom analyses to determine two other fuel oxygenates--ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME). The NWQL was not able to obtain a reference standard for tert-amyl ethyl ether (TAEE), another possible fuel oxygenate (Shelley and Fouhy, 1994, p. 63). The shallow ground-water samples were collected as part of the USGS National Water-Quality Assessment Program. These samples were collected from 211 urban wells or springs and 562 agricultural wells sampled by the USGS in 1993 and 1994. The wells were keyed to specific land-use areas to assess the effects of different uses on ground-water quality (Squillace and others, 1995, p. 2). Ground-water samples were preserved on site to pH less than or equal to 2 with a solution of 1:1 hydrochloric acid. All samples were analyzed at the NWQL within 2 weeks after collection. The purpose of this fact sheet is to explain briefly the analytical method implemented by the USGS for determining MTBE and other fuel oxygenates. The scope is necessarily limited to an overview of the analytical method (instrumentation, sample preparation, calibration and quantitation, identification, and preservation of samples) and method performance (reagent blanks, accuracy, and precision).

Influence of viral infection on essential oil composition of Ocimum basilicum (Lamiaceae).

PubMed

Nagai, Alice; Duarte, Ligia M L; Santos, Déborah Y A C

2011-08-01

Ocimum basilicum L., popularly known as sweet basil, is a Lamiaceae species whose essential oil is mainly composed of monoterpenes, sesquiterpenes and phenylpropanoids. The contents of these compounds can be affected by abiotic and biotic factors such as infections caused by viruses. The main goal of this research was an investigation of the effects of viral infection on the essential oil profile of common basil. Seeds of O. basilicum L. cv. Genovese were sowed and kept in a greenhouse. Plants presenting two pairs of leaves above the cotyledons were inoculated with an unidentified virus isolated from a field plant showing chlorotic yellow spots and foliar deformation. Essential oils of healthy and infected plants were extracted by hydrodistillation and analyzed by GCMS. Changes in essential oil composition due to viral infection were observed. Methyleugenol and p-cresol,2,6-di-tert-butyl were the main constituents. However, methyleugenol contents were significantly decreased in infected plants.

Nonadiabatic small-polaron hopping electron transport in diphenoquinone-doped polycarbonate

NASA Astrophysics Data System (ADS)

Yamaguchi, Yasuhiro; Yokoyama, Masaaki

1991-10-01

The dependences of electron mobility on the electric field F, temperature T, and hopping site distance R have been characterized in 3,5-dimethyl-3',5'-di-tert-butyl-4,4'-diphenoquinone dispersed molecularly in a polycarbonate according to Schein's analytical technique. The electron mobility can be described in the form a0R2 exp(-2R/R0) exp(-E0/kT) × exp[β(1/kT-1/kT0)F1/2], where a0, R0, β, and T0 are constants. Moreover, it is found that the zero-field activation energy E0 is independent of R. The invariable E0 and the exponential dependence of the Arrhenius prefactor on R strongly suggest that the electron transport therein is due to nonadiabatic small-polaron hopping. Based on the small-polaron theory, the transport properties are qualitatively discussed in terms of molecular properties.

Evaluation of the anti-oxidative effect (in vitro) of tea polyphenols.

PubMed

Hashimoto, Fumio; Ono, Masateru; Masuoka, Chikako; Ito, Yasuyuki; Sakata, Yusuke; Shimizu, Keiichi; Nonaka, Gen-ichiro; Nishioka, Itsuo; Nohara, Toshihiro

2003-02-01

Forty-three polyphenols from tea leaves were evaluated for their anti-oxidative effect against lipid peroxidation by the ferric thiocyanate method in vitro. Among these, 1,4,6-tri-O-galloyl-beta-D-glucose (hydrolyzable tannin) showed the highest anti-oxidative activity against lipid peroxidation, even stronger than that of 3-tert.-butyl-4-hydroxyanisole (BHA). The assay demonstrates that tea polyphenols, except for desgalloylated dimeric proanthocyanidins that possess a catechin structure in the upper unit and desgalloylated flavan-3-ols, and excepting theaflavin 3,3'-di-O-gallate, had more anti-oxidative activity than that of alpha-tocopherol. The chemical structure-activity relationship shows that the anti-oxidative action advanced with the condensation of two molecules of flavan-3-ols as well as with 3-O-acylation in the flavan skeleton such as that by galloyl, (3'-O-methyl)-galloyl, and p-coumaroyl groups.

Silver Nanoparticles Synthesized by Decomposition of a Silver Organic Complex with Valence Tautomerism and Their Properties

NASA Astrophysics Data System (ADS)

Harbatsevich, H. I.; Loginova, N. V.; Koval‧chuk, T. V.; Osipovich, N. P.; Gres, A. T.

2017-03-01

Features of the formation of silver nanoparticles (Ag-NPs) via intramolecular redox transformation of the Ag(I) complex of 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde isonicotinoylhydrazone in organic solvents with donor numbers DN > 19 were studied. The stability of the organic sols depended on the nature of the dispersion medium and the presence of oxygen and water in it. The physical chemistry and morphology of the Ag-NP in the organic sol were investigated using molecular absorption spectroscopy, transmission electron microscopy, and atomic force microscopy. The silver sol consisted of spherical Ag-NPs 5-20 nm in size with a characteristic absorption band near 440 nm. It was found that the silver complex with valence tautomerism was a promising precursor for Ag-NPs. The synthesized Ag-NPs showed high antimicrobial activity compared with standard antibiotics and Ag-containing agents (MIC = 0.007 μmol/mL).

A novel colorimetric probe derived from isonicotic acid hydrazide for copper (II) determination based on internal charge transfer (ICT).

PubMed

Liu, Qing; Fei, Qiang; Fei, Yanqun; Fan, Qian; Shan, Hongyan; Feng, Guodong; Huan, Yanfu

2015-12-05

A novel isonicotic acid hydrazide Schiff base derivative N'-(3,5-di-tert-butyl-2-hydroxy-benzylidene) isonicotinohydrazide (DHIH) has been synthesized and developed as a high selective and sensitive colorimetric probe for Cu(2+) determination. Addition of Cu(2+) to the solution of DHIH resulted in a rapid color change from colorless to yellow together with an obvious new absorption band appeared at the range of 400-440 nm by forming a 1:1 complex. Experimental results indicated that the DHIH could provide absorption response to Cu(2+) with a linear dynamic range from 1.0×10(-5) to 1.0×10(-4)mol/L. The detection limit of Cu(2+) was 5.24×10(-7)mol/L with good tolerance of other metal ions. Copyright © 2015 Elsevier B.V. All rights reserved.

Bis(1,3-di-tert-butylimidazolin-2-iminato) titanium complexes as effective catalysts for the monodisperse polymerization of propylene.

PubMed

Sharma, Manab; Yameen, Haneen Simaan; Tumanskii, Boris; Filimon, Sabina-Alexandra; Tamm, Matthias; Eisen, Moris S

2012-10-17

The use of bis(1,3-di-tert-butylimidazolin-2-iminato) titanium dichloride (1) and dimethyl (2) complexes in the polymerization of propylene is presented. The complexes were activated using different amounts of methylalumoxane (MAO), giving in each case a very active catalytic mixture and producing polymers with a narrow molecular weight distribution (polydispersity = 1.10). The use of the cocatalyst triphenylcarbenium (trityl) tetra(pentafluorophenyl)borate totally inhibits the reaction, producing the corresponding bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(III) methyl complex, the trityl radical ((•)CPh(3)), the anionic MeB(C(6)F(5))(4)(-), B(C(6)F(5))(3), and the bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(IV) dimethyl·B(C(6)F(5))(3) complex. The use of a combination of physical methods such as NMR, ESR-C(60), and MALDI-TOF analyses enabled us to propose a plausible mechanism for the polymerization of propylene, presenting that the polymerization is mainly carried out in a living fashion. In addition, we present a slow equilibrium toward a small amount of a dormant species responsible for 2,1-misinsertions and chain transfer processes.

Redox behavior and biological properties of ferrocene bearing porphyrins.

PubMed

Lippert, Rainer; Shubina, Tatyana E; Vojnovic, Sandra; Pavic, Aleksandar; Veselinovic, Jovana; Nikodinovic-Runic, Jasmina; Stankovic, Nada; Ivanović-Burmazović, Ivana

2017-06-01

In order to improve antimicrobial effects of previously studied meso-tetrakis(4-ferrocenylphenyl)porphyrin 1, we have modified its structure by replacing two trans-positioned ferrocenylphenyl moieties with methoxy methylene substituted tert-butylphenyl moieties. Newly synthesized 5 4 ,15 4 -bis-(ferrocenyl)-10 4 ,20 4 -bis-(tert-butyl)-10 2 ,10 6 ,20 2 ,20 6 -tetrakis-(methoxy-methylene)-5,10,15,20-tetraphenylporphyrin 4 was chemically characterized in detail (by NMR, UV/Vis, IR, MALDI-TOF and ESI MS spectrometry, cyclic voltammetry, prediction of the relative lipophilicity as well as computational methods) and its biological effects were studied in terms of its antibacterial and antifungal activity (both with and without photoactivation), cytotoxicity, hemolysis and DNA cleavage. New ferrocene bearing porphyrin 4 has demonstrated a broader antimicrobial spectrum and modified effects on eukaryotic cells compared to 1. This was discussed in terms of its i) increased lipophilicity, while exhibiting lower toxicity, and ii) the redox potential of a two-electron process that is shifted to lower values, in comparison to ferrocene, thus, entering the physiologically available range and being activated towards redox interactions with biomolecules. Copyright © 2017 Elsevier Inc. All rights reserved.

Research on Volatile Organic Compounds From Bacillus subtilis CF-3: Biocontrol Effects on Fruit Fungal Pathogens and Dynamic Changes During Fermentation

PubMed Central

Gao, Haiyan; Li, Peizhong; Xu, Xinxing; Zeng, Qing; Guan, Wenqiang

2018-01-01

The dynamic changes of the levels of volatile organic compounds (VOCs) produced by Bacillus subtilis CF-3 and their biocontrol effects on common fungal pathogens were researched in this study. The results showed that the VOCs in 24-h fermentation liquid (24hFL) of B. subtilis CF-3 inhibited mycelial growth of Botrytis cinerea, Colletotrichum gloeosporioides, Penicillium expansum, Monilinia fructicola, and Alternaria alternata, with a mean inhibition rate of 59.97%. The inhibitory effect on M. fructicola and C. gloeosporioides was the highest; they were therefore selected as target fungal pathogens for further experiments. Based on headspace solid-phase microextraction combined with gas chromatography-mass spectrometry (HS-SPME-GC-MS), 74 potential VOCs were identified during the fermentation: 15 alcohols, 18 ketones, 4 pyrazines, 4 esters, 10 acids, 5 phenols, 3 hydrocarbons, 3 amines, 2 aldehydes, 5 ethers, and 5 other components. At different fermentation times, the type and content of VOCs were different. Most of the potential VOCs (62 VOCs) were identified in the 48hFL. The inhibition rates of all VOCs reached their peaks (73.46% on M. fructicola and 63.63% on C. gloeosporioides) in the 24hFL. Among the identified VOCs, 2,4-di-tert-butylphenol, 1-octanol, and benzothiazole showed significant positive correlations with the rates of M. fructicola and C. gloeosporioides inhibition. Benzoic acid and benzaldehyde showed a significant positive correlation with the rates of M. fructicola inhibition, and anisole and 3-methylbutanal showed a significant positive correlation with the rates of C. gloeosporioides inhibition. In vitro, 2,4-di-tert-butylphenol showed a strong inhibitory effect on both M. fructicola and C. gloeosporioides. In vivo, benzothiazole showed the strongest inhibitory effect on the mycelial extensions of both M. fructicola and C. gloeosporioides, which also led to an increased rate of healthy fruit. The results of the present study clarified that 2,4-di-tert-butylthiophenol and benzothiazole are key inhibitory VOCs produced by B. subtilis CF-3. PMID:29593695

CHLORINATED SOLVENT PLUME CONTROL

EPA Science Inventory

This lecture will cover recent success in controlling and assessing the treatment of shallow ground water plumes of chlorinated solvents, other halogenated organic compounds, and methyl tert-butyl ether (MTBE).

Phenolic aminocarboxylate chelates of 99mTc as hepatobiliary agents.

PubMed

Hunt, F C; Maddalena, D J; Wilson, J G; Bautovich, G J

1986-01-01

A series of alkyl- and halogen-substituted derivatives of ethylenediamine di[o-hydroxyphenylacetic acid] (EDDHA) and N,N'-bis[2-hydroxybenzyl] ethylenediamine N,N'-diacetic acid (HBED) were complexed with 99mTc and their biodistribution was determined in rats. All complexes displayed substantial hepatobiliary excretion; of each series, 99mTc-Br-EDDHA and 99mTc-di-Cl-HBED had the maximum amount in the gastrointestinal tract. Scintigraphic studies of 99mTc-Cl-EDDHA in dogs revealed prompt imaging of the liver followed by imaging of the gall bladder as the complex was excreted into the bile.

40 CFR 463.33 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... limitations guidelines for bis(2-ethylhexyl) phthalate, di-n-butyl phthalate, and dimethyl phthalate are reserved. (b) The Agency has determined that, with the exception of bis(2-ethylhexyl) phthalate, di-n-butyl...

Enhanced cometabolic degradation of methyl tert-butyl ether by a Pseudomonas sp. strain grown on n-pentane

NASA Astrophysics Data System (ADS)

Li, S. S.; Wang, S.; Yan, W.

2016-08-01

When methyl tert-butyl ether (MTBE) is added as oxygenates it increases the octane number and decreases the release of nitric oxide from the incomplete combustion of reformulated gasoline. The extensive use of MTBE allowed it to be detectable as a pollutant in both ground-level and underground water worldwide. The present study focuses on the isolation and characterization of MTB-degrading microorganisms by cometabolism based on the results of growth on different carbon sources. It also focuses on the kinetic analysis and the continuous degradation of MTBE. A bacterial strain WL1 that can grow on both n-alkanes (C5-C8) and aromatics was isolated and named Pseudomonas sp. WL1 according to the 16S rDNA sequencing analysis. Strain WL1 could cometabolically degrade MTBE in the presence of n-alkanes with a desirable degradation rate. Diverse n-alkanes with different lengths of carbon chains showed significant influence on the degradation rate of MTBE and accumulation of tert-butyl alcohol (TBA). When strain WL1 cometabolically degraded MTBE in the presence of n-pentane, higher MTBE-degrading rate and lower TBA-accumulation were observed (Vmax = 38.1 nmol/min/mgprotei, Ks = 6.8 mmol/L). In the continuous degrading experiment, the removal efficiency of MTBE by Pseudomonas sp. WL1 did not show any obvious decrease after five subsequent additions.

Microbial community composition during anaerobic mineralization of tert-butyl alcohol (TBA) in fuel-contaminated aquifer material.

PubMed

Wei, Na; Finneran, Kevin T

2011-04-01

Anaerobic mineralization of tert-butyl alcohol (TBA) and methyl tert-butyl ether (MTBE) were studied in sediment incubations prepared with fuel-contaminated aquifer material. Microbial community compositions in all incubations were characterized by amplified ribosomal DNA restriction analysis (ARDRA). The aquifer material mineralized 42.3±9.9% of [U-(14)C]-TBA to 14CO2 without electron acceptor amendment. Fe(III), sulfate, and Fe(III) plus anthraquinone-2,6-disulfonate addition also promoted U-[14C]-TBA mineralization at levels similar to those of the unamended controls. Nitrate actually inhibited TBA mineralization relative to unamended controls. In contrast to TBA, [U-(14)C]-MTBE was not significantly mineralized in 400 days regardless of electron acceptor amendment. Microbial community analysis indicated that the abundance of one dominant clone group correlated closely with anaerobic TBA mineralization. The clone was phylogenetically distinct from known aerobic TBA-degrading microorganisms, Fe(III)- or sulfate-reducing bacteria. It was most closely associated with organisms belonging to the alphaproteobacteria. Microbial communities were different in MTBE and TBA amended incubations. Shannon indices and Simpson indices (statistical community comparison tools) both demonstrated that microbial community diversity decreased in incubations actively mineralizing TBA, with distinct "dominant" clones developing. These data contribute to our understanding of anaerobic microbial transformation of fuel oxygenates in contaminated aquifer material and the organisms that may catalyze the reactions.

Spectroscopic investigation of H atom transfer in a gas-phase dissociation reaction: McLafferty rearrangement of model gas-phase peptide ions.

PubMed

Van Stipdonk, Michael J; Kerstetter, Dale R; Leavitt, Christopher M; Groenewold, Gary S; Steill, Jeffrey; Oomens, Jos

2008-06-14

Wavelength-selective infrared multiple-photon photodissociation (WS-IRMPD) was used to study isotopically-labeled ions generated by McLafferty rearrangement of nicotinyl-glycine-tert-butyl ester and betaine-glycine-tert-butyl ester. The tert-butyl esters were incubated in a mixture of D(2)O and CH(3)OD to induce solution-phase hydrogen-deuterium exchange and then converted to gas-phase ions using electrospray ionization. McLafferty rearrangement was used to generate the free-acid forms of the respective model peptides through transfer of an H atom and elimination of butene. The specific aim was to use vibrational spectra generated by WS-IRMPD to determine whether the H atom remains at the acid group, or migrates to one or more of the other exchangeable sites. Comparison of the IRMPD results in the region from 1200-1900 cm(-1) to theoretical spectra for different isotopically-labeled isomers clearly shows that the H atom is situated at the C-terminal acid group and migration to amide positions is negligible on the time scale of the experiment. The results of this study suggest that use of the McLafferty rearrangement for peptide esters could be an effective approach for generation of H-atom isotope tracers, in situ, for subsequent investigation of intramolecular proton migration during peptide fragmentation studies.

Biosynthesis of tert-butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate by carbonyl reductase from Rhodosporidium toruloides in mono and biphasic media.

PubMed

Liu, Zhi-Qiang; Wu, Lin; Zheng, Ling; Wang, Wen-Zhong; Zhang, Xiao-Jian; Jin, Li-Qun; Zheng, Yu-Guo

2018-02-01

tert-Butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate ((3R,5S)-CDHH) is the key intermediate for synthesis of atorvastatin and rosuvastatin. Carbonyl reductase exhibits excellent activity toward tert-butyl (S)-6-chloro-5-hydroxy-3-oxohexanoate ((S)-CHOH) to synthesize (3R,5S)-CDHH. In this study, a whole cell biosynthesis reaction system to produce (3R,5S)-CDHH was constructed in organic solvents. A solution of 10% (v/v) Tween-80 was introduced to the reaction system as a co-solvent, which greatly enhanced biotransformation process, giving 98.9% yield, >99% ee and 1.8-fold higher space time yield in 5 h bioconversion of 1 M (S)-CHOH, compared with 98.7% yield and >99% ee in 9 h bioconversion of a purely aqueous reaction system. Moreover, a water-octanol biphasic reaction system was built and 20% of octanol was added as reservoir of substrate resulting in 98% yield, >99% ee and 4.08 mmol L -1  h -1  g -1 (wet cell weight) space time yield. This study paved a way for the whole cell biosynthesis of (3R,5S)-CDHH in mono and biphasic media. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cultivation of Aquincola tertiaricarbonis L108 on the fuel oxygenate intermediate tert-butyl alcohol induces aerobic anoxygenic photosynthesis at extremely low feeding rates.

PubMed

Rohwerder, Thore; Müller, Roland H; Weichler, M Teresa; Schuster, Judith; Hübschmann, Thomas; Müller, Susann; Harms, Hauke

2013-10-01

Aerobic anoxygenic photosynthesis (AAP) is found in an increasing number of proteobacterial strains thriving in ecosystems ranging from extremely oligotrophic to eutrophic. Here, we have investigated whether the fuel oxygenate-degrading betaproteobacterium Aquincola tertiaricarbonis L108 can use AAP to compensate kinetic limitations at low heterotrophic substrate fluxes. In a fermenter experiment with complete biomass retention and also during chemostat cultivation, strain L108 was challenged with extremely low substrate feeding rates of tert-butyl alcohol (TBA), an intermediate of methyl tert-butyl ether (MTBE). Interestingly, formation of photosynthetic pigments, identified as bacteriochlorophyll a and spirilloxanthin, was only induced in growing cells at TBA feeding rates less than or equal to maintenance requirements observed under energy excess conditions. Growth continued at rates between 0.001 and 0.002 h(-1) even when the TBA feed was decreased to values close to 30 % of this maintenance rate. Partial sequencing of genomic DNA of strain L108 revealed a bacteriochlorophyll synthesis gene cluster (bchFNBHL) and photosynthesis regulator genes (ppsR and ppaA) typically found in AAP and other photosynthetic proteobacteria. The usage of light as auxiliary energy source enabling evolution of efficient degradation pathways for kinetically limited heterotrophic substrates and for lowering the threshold substrate concentration Smin at which growth becomes zero is discussed.

A comparison of the efficacy of various antioxidants on the oxidative stability of irradiated polyethylene.

PubMed

Hope, Natalie; Bellare, Anuj

2015-03-01

Ultrahigh-molecular-weight polyethylene (UHMWPE) is subjected to radiation crosslinking to form highly crosslinked polyethylene (HXLPE), which has improved wear resistance. First-generation HXLPE was subjected to thermal treatment to reduce or quench free radicals that can induce long-term oxidative degeneration. Most recently, antioxidants have been added to HXLPE to induce oxidative resistance rather than by thermal treatment. However, antioxidants can interfere with the efficiency of radiation crosslinking. We sought to identify (1) which antioxidant from among those tested (vitamin E, β-carotene, butylated hydroxytoluene, or pentaerythritol tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) causes the least reduction of crosslinking; (2) which promotes the greatest oxidative stability; and (3) which had the lowest ratio of oxidation index to crosslink density. Medical-grade polyethylene (PE) resin was blended with 0.1 weight % of the following stabilizers: alpha tocopherol (vitamin E), β-carotene, butylated hydroxytoluene (BHT), and pentaerythritol tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (a hindered phenol antioxidant [HPAO]). These blends were compression-molded into sheets and subjected to electron beam irradiation to a dose of 100 kGy. Equilibrium swelling experiments were conducted to calculate crosslink density. Each PE was subjected to accelerated aging for a period of 2 weeks and Fourier transform infrared spectroscopy was used to measure the maximum oxidation. Statistical analysis was conducted using analysis of variance with Fisher's protected least significant difference in which a p value of < 0.05 was used to define a significant difference. The least reduction of crosslinking in antioxidant-containing HXLPE was observed with HPAO, which had a crosslink density (n = 6) of 0.167 (effect size [ES] = 0.87; 95% confidence interval [CI], 0.162-0.173) mol/dm(3) compared with 0.139 (ES = 1.57; 95% CI, 0.132-0.146) mol/dm(3) (p = 0.020) for BHT, 0.131 (ES = 1.77; 95% CI, 0.123-0.139) mol/dm(3) (p = 0.004) for β-carotene, and 0.130 (ES = 1.79; 95% CI, 0.124-0.136) mol/dm(3) (p = 0.003) for vitamin E, whereas pure HXLPE had a crosslink density of 0.203 (95% CI, 0.170-0.235) mol/dm(3) (p = 0.005). BHT-PE had an oxidation index of 0.21 (ES = 13.14; 95% CI, 0.19-0.22) followed by HPAO-PE, vitamin E-PE and β-carotene-PE, which had oxidation indices of 0.28 (ES = 9.68; 95% CI, 0.28-0.29), 0.29 (ES = 9.59; 95% CI, 0.27-0.30), and 0.35 (ES = 6.68; 95% CI, 0.34-0.37), respectively (p < 0.001 for all groups). BHT-PE had the lowest ratio of oxidation index to crosslink density of the materials tested (1.49, ES = 1.94; 95% CI, 1.32-1.66) followed by HPAO-PE (1.70, ES = 1.52; 95% CI, 1.61-1.80), vitamin E-PE (2.21, ES = 0.52; 95% CI, 2.05-2.38), and β-carotene-PE (2.69, ES = -0.43; 95% CI, 2.46-2.93) compared with control PE (2.47, 95% CI, 2.07-2.88) with β-carotene (p = 0.208) and vitamin E (p = 0.129) not being different from the control. BHT-modified HXLPE was found in this study to have the lowest oxidation index as well as the lowest ratio of oxidation index to crosslink density compared with vitamin E, HPAO, and β-carotene-modified HXLPEs. More comprehensive studies are required such as wear testing using joint simulators as well as biocompatibility studies before BHT-modified HXLPE can be considered for clinical use. BHT is a synthetic antioxidant commonly used in the polymer industry to prevent long-term oxidative degradation and has been approved by the FDA for use in cosmetics and foodstuffs. It may be an attractive potential stabilizer for HXLPE in total joint replacements.

Thermodynamic properties of hyperbranched polymer, Boltorn U3000, using inverse gas chromatography.

PubMed

Domańska, Urszula; Zołek-Tryznowska, Zuzanna

2009-11-19

Mass-fraction activity coefficients at infinite dilution (Omega13(infinity)) of alkanes (C5-C10), cycloalkanes (C5-C8), alkenes (C5-C8), alkynes (C5-C8), aromatic hydrocarbons (benzene, toluene, ethylbenzene, o-, m-, p-xylene, thiophene), alcohols (C1-C5), water, ethers (tetrahydrofuran (THF), methyl-tert-butylether (MTBE), diethyl-, di-n-propyl-, di-n-butyl ether), and ketones (propanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclopentanone) in the hyperbranched polymer, Boltorn U3000 (B-U3000), have been determined by inverse gas chromatography (IGC) using the polymer as the stationary phase. The measurements were carried out at different temperatures between 308.15 and 348.15 K. The density and thermophysical properties of polymer were described. The specific retention volume (V(g)), the Flory-Huggins interaction parameter (chi13(infinity)), the molar enthalpy of sorption (the partial molar enthalpies of solute dissolution) (Delta(s)H), the partial molar excess enthalpy at infinite dilution of the solute and polymer (DeltaH1(E,infinity)), the partial molar Gibbs excess energy at infinite dilution (DeltaG1(E,infinity)), and the solubility parameter (delta3) were calculated.

Structural motifs of diiodine complexes with amides and thioamides.

PubMed

Parigoridi, Ioanna-Efpraxia; Corban, Ghada J; Hadjikakou, Sotiris K; Hadjiliadis, Nick; Kourkoumelis, Nikolaos; Kostakis, George; Psycharis, Vassilis; Raptopoulou, Catherine P; Kubicki, Maciej

2008-10-14

The reaction of 2-pyrimidone hydrochloride ([C(4)H(5)N(2)O](+)[Cl](-) or [PMOH(2)](+)[Cl](-)) with diiodine in a dichloromethane-methanol solution resulted in the formation of ([C(4)H(5)N(2)O](+))(2)[I(2)Cl(2)](2-) (1) complex. The compound was characterized by elemental analysis, FT-IR, DTA-TG and conductivity titrations. The crystal structure of 1 was also determined by X-ray diffraction at 294(1) K. Compound 1 is monoclinic, space group P2(1)/n, consisting of two cationic [PMOH(2)](+) species and a [I(2)Cl(2)](2-) counter dianion. The cation is in its keto form. Direct reaction of thiazolidine-2-thione (tzdtH), with diiodine in dichloromethane solution, on the other hand, led to the formation of a crystalline solid which contained two complexes of formulae [(tzdtH)(2)I](+)[I(3)](-).2I(2) (2) and [(tzdtH)I(2)](2).I(2) (2a) in a ratio of 90 to 10%. Complex 2a was characterized by X-ray analysis at 180(2) K. Compound is monoclinic, space group C2/c and contains two units of [(tzdtH)I(2)] "spoke" structures. Compound 1, as well as the known species iodonium salt [(tzdtH)(2)I](+)[I(3)](-).2I(2) (2) and the charge transfer (CT) iodine complexes of formulae [(bztzdtH)I(2)] (3) and [(bztzdtH)I(2)].I(2) (4) (bztzdtH = 2-mercaptobenzothiazole) with "spoke" and extended "spoke" structures respectively, were tested for their oxidizing activity towards 3,5-di-tert-butylcatechol to 3,5-di-tert-butyl-o-benzoquinone.

An Investigation into the Physico-chemical Properties of Transformer Oil Blends with Antioxidants extracted from Turmeric Powder

NASA Astrophysics Data System (ADS)

Dukhi, Veresha; Bissessur, Ajay; Ngila, Catherine Jane; Ijumba, Nelson Mutatina

2013-07-01

The blending of transformer oil (used mainly as an insulating oil) with appropriate synthetic antioxidants, such as BHT (2,6-di-tert-butyl-4-methylphenol) and DBP (2,6-di-tert-butylphenol) have been previously reported. This article is focused on the use of antioxidant extracts from turmeric (Curcuma longa), a natural source. Turmeric is well known for its antimicrobial, antioxidant and anticarcinogenic properties owing to the active nature of its components. Extracts from powdered turmeric were subsequently blended into naphthenic-based uninhibited virgin transformer oil, hereinafter referred to as extract-oil blends (E-OB). Thin-layer chromatography (TLC) of the oil blends revealed that five components extracted from turmeric powder were successfully blended into the oil. Subsequent gas chromatography-mass spectrometry (GC-MS) analysis confirmed the presence of the compounds: curcumene, sesquiphellandrene, ar-turmerone, turmerone and curlone. Thermogravimetric analysis (TGA) of the extract-oil blends, containing various levels of extracts, revealed an average temperature shift of ˜8.21°C in the initial onset of degradation in comparison to virgin non-blended oil. The 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay showed that an increase in the mass aliquot of turmeric extracts in the transformer oil increased the free radical scavenging activity of the oil. Electrical properties of the oil investigated showed that the dissipation factor in the blended oil was found to be lower than that of virgin transformer oil. Evidently, a lower dissipation value renders the oil blend as a superior insulator over normal virgin non-blended oil. This investigation elucidated improved physico-chemical properties of transformer oil blended with turmeric antioxidant extracts.

Bimetallic iron–iron and iron–zinc complexes of the redox-active ONO pincer ligand† †Electronic supplementary information (ESI) available: Complete experimental procedures and magnetic measurements and models. CCDC 1417565–1417567. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03006d Click here for additional data file. Click here for additional data file.

PubMed Central

Wong, Janice L.; Higgins, Robert F.; Bhowmick, Indrani; Cao, David Xi; Szigethy, Géza; Ziller, Joseph W.

2016-01-01

A new bimetallic platform comprising a six-coordinate Fe(ONO)2 unit bound to an (ONO)M (M = Fe, Zn) has been discovered ((ONOcat)H3 = bis(3,5-di-tert-butyl-2-phenol)amine). Reaction of Fe(ONO)2 with either (ONOcat)Fe(py)3 or with (ONOq)FeCl2 under reducing conditions led to the formation of the bimetallic complex Fe2(ONO)3, which includes unique five- and six-coordinate iron centers. Similarly, the reaction of Fe(ONO)2 with the new synthon (ONOsq˙)Zn(py)2 led to the formation of the heterobimetallic complex FeZn(ONO)3, with a six-coordinate iron center and a five-coordinate zinc center. Both bimetallic complexes were characterized by single-crystal X-ray diffraction studies, solid-state magnetic measurements, and multiple spectroscopic techniques. The magnetic data for FeZn(ONO)3 are consistent with a ground state S = 3/2 spin system, generated from a high-spin iron(ii) center that is antiferromagnetically coupled to a single (ONOsq˙)2– radical ligand. In the case of Fe2(ONO)3, the magnetic data revealed a ground state S = 7/2 spin system arising from the interactions of one high-spin iron(ii) center, one high-spin iron(iii) center, and two (ONOsq˙)2– radical ligands. PMID:28808535

Application of a source apportionment model in consideration of volatile organic compounds in an urban stream

USGS Publications Warehouse

Asher, W.E.; Luo, W.; Campo, K.W.; Bender, D.A.; Robinson, K.W.; Zogorski, J.S.; Pankow, J.F.

2007-01-01

Position-dependent concentrations of trichloroethylene and methyl-tert-butyl ether are considered for a 2.81-km section of the Aberjona River in Massachusetts, USA. This river flows through Woburn and Winchester (Massachusetts, USA), an area that is highly urbanized, has a long history of industrial activities dating to the early 1800s, and has gained national attention because of contamination from chlorinated solvent compounds in Woburn wells G and H. The river study section is in Winchester and begins approximately five stream kilometers downstream from the Woburn wells superfund site. Approximately 300 toxic release sites are documented in the watershed upstream from the terminus of the study section. The inflow to the river study section is considered one source of contamination. Other sources are the atmosphere, a tributary flow, and groundwater flows entering the river; the latter are categorized according to stream zone (1, 2, 3, etc.). Loss processes considered include outflows to groundwater and water-to-atmosphere transfer of volatile compounds. For both trichloroethylene and methyl-rerf-butyl ether, degradation is neglected over the timescale of interest. Source apportionment fractions with assigned values ??inflow, ??1, ??2, ??3, etc. are tracked by a source apportionment model. The strengths of the groundwater and tributary sources serve as fitting parameters when minimizing a reduced least squares statistic between water concentrations measured during a synoptic study in July 2001 versus predictions from the model. The model fits provide strong evidence of substantial unknown groundwater sources of trichloroethylene and methyl-tert-butyl ether amounting to tens of grams per day of trichloroethylene and methyl-tert-butyl ether in the river along the study section. Modeling in a source apportionment manner can be useful to water quality managers allocating limited resources for remediation and source control. ?? 2007 SETAC.

Electrochemical detection of phenolic estrogenic compounds at clay modified carbon paste electrode

NASA Astrophysics Data System (ADS)

Belkamssa, N.; Ouattara, L.; Kawachi, A.; Tsujimura, M.; Isoda, H.; Chtaini, A.; Ksibi, M.

2015-04-01

A simple and sensitive electroanalytical method was developed to determine the Endocrine Disrupting chemical 4-tert-octylphenol on clay modified carbon paste electrode (Clay/CPE). The electrochemical response of the proposed electrode was studied by means of cyclic and square wave voltammetry. It has found that the oxidation of 4-tert-octylphenol on the clay/CPE displayed a well-defined oxidation peak. Under these optimal conditions, a linear relation between concentrations of 4-tert-octylphenol current response was obtained over range of 7.26×10-6 to 3.87×10-7 with a detection and quantification limit of 9.2×10-7 M and 3.06×10-6 M, respectively. The correlation coefficient is 0.9963. The modified electrode showed suitable sensitivity, high stability and an accurate detection of 4-tert-octylphenol. The modified electrode also relevant suitable selectivity for various phenolic estrogenic compounds.

40 CFR Appendix - Tables to Part 132

Code of Federal Regulations, 2014 CFR

2014-07-01

... ether Butyl benzyl phthalate Cadmium Carbon tetrachloride; tetrachloromethane Chlorobenzene p-Chloro-m... Copper Cyanide 2,4-D; 2,4-Dichlorophenoxyacetic acid DEHP; di(2-ethylhexyl) phthalate Diazinon 1,2:5,6-Dibenzanthracene; dibenz[a,h]anthracene Dibutyl phthalate; di-n-butyl phthalate 1,2-Dichlorobenzene 1,3...

Disposition and pharmacokinetics of a lubricant contaminant, 2,6-di-tert-butyl 4-nitrophenol, in grafted human skin.

PubMed

Pershing, Lynn K; Nelson, Joel L; Corlett, Judy L; Briggs, G Bruce; Still, Kenneth R; Jederberg, Warren W

2006-01-01

Disposition and uptake/elimination profiles of topical 2,6-di-t-butyl, 4-nitrophenol (DBNP), the nitrated metabolite of an antioxidant additive of lubricant and hydraulic fluids was quantified in human skin grafted on athymic mice after a single topical 75 microg dose in corn oil. DBNP was quantified throughout the stratum corneum (SC), epidermis (E) and dermis (D) in punch biopsies collected from treated skin 0.5, 1, 2, 4, 8 and 24 h after application. SC samples were harvested from the treated skin with 20 adhesive discs. E and D were generated from the biopsy using a manual sectioning method. Detectable DBNP concentrations were measured in all skin compartments at all time points investigated. The Cmax of DBNP in SC was 1663 +/- 602 microg cm(-3), and approximately 30 and approximately 300 fold greater than the Cmax for E and D, respectively. Tmax occurred at 1.0, 0.5 and 1.0 in the SC, E and D, respectively. Over a 24 h interval (AUC0-24 h) there was 52 and 520 fold more DBNP in the SC than E and D, respectively. The elimination half-life of DBNP was 11 h from the SC and 9 h from both E and D. Thus, DBNP was quickly absorbed into the outermost layer of skin and established a steep concentration profile through human skin. The data are consistent with the vast majority of DBNP remaining on the surface (77%) or within human skin (15%) in vivo with only 0.2% of the DBNP dose quantified in the systemic blood circulation. Copyright 2006 John Wiley & Sons, Ltd.

Near-IR core-substituted naphthalenediimide fluorescent chemosensors for zinc ions: ligand effects on PET and ICT channels.

PubMed

Lu, Xinyu; Zhu, Weihong; Xie, Yongshu; Li, Xin; Gao, Yuan; Li, Fuyou; Tian, He

2010-07-26

Near-IR (NIR) emission can offer distinct advantages for both in vitro and in vivo biological applications. Two NIR fluorescent turn-on sensors N,N'-di-n-butyl-2-(N-{2-[bis(pyridin-2-ylmethyl)amino]ethyl})-6-(N-piperidinyl)naphthalene-1,4,5,8-tetracarboxylic acid bisimide and N,N'-di- n-butyl-2-[N,N,N'-tri(pyridin-2-ylmethyl)amino]ethyl-6-(N-piperidinyl)naphthalene-1,4,5,8-tetracarboxylic acid bisimide (PND and PNT) for Zn(2+) based on naphthalenediimide fluorophore are reported. Our strategy was to choose core-substituted naphthalenediimide (NDI) as a novel NIR fluorophore and N,N-di(pyridin-2-ylmethyl)ethane-1,2-diamine (DPEA) or N,N,N'-tri(pyridin-2-ylmethyl)ethane-1,2-diamine (TPEA) as the receptor, respectively, so as to improve the selectivity to Zn(2+). In the case of PND, the negligible shift in absorption and emission spectra is strongly suggestive that the secondary nitrogen atom (directly connected to the NDI moiety, N(1)) is little disturbed with Zn(2+). The fluorescence enhancement of PND with Zn(2+) titration is dominated with a typical photoinduced electron-transfer (PET) process. In contrast, the N(1) atom for PNT can participate in the coordination of Zn(2+) ion, diminishing the electron delocalization of the NDI moiety and resulting in intramolecular charge-transfer (ICT) disturbance. For PNT, the distinct blueshift in both absorbance and fluorescence is indicative of a combination of PET and ICT processes, which unexpectedly decreases the sensitivity to Zn(2+). Due to the differential binding mode caused by the ligand effect, PND shows excellent selectivity to Zn(2+) over other metal ions, with a larger fluorescent enhancement centered at 650 nm. Also both PND and PNT were successfully used to image intracellular Zn(2+) ions in the living KB cells.

Organophosphazenes. 15. Reactions of Hexafluorocyclotriphosphazene with Tert- and n-Butyl Lithium Reagents

DTIC Science & Technology

1981-12-04

H ECU’ITY CLASSIFICATION OF THIS PAGE (When frl,* IFnfered) REPORT DOCUMENTATION PAGE - RE INSTRUCTIONSBEFORE COMPLETING FORM 1. REPORT NUMBER 2...GOVT ACCESSION NO. 3. RECIPIENT’S CATALOG NUMBER 10 _ _ _ _V11 * 4. TITLE (and Subtitle) S. TYPE OF REPORT I PERIOD COVERED Organoohosphazenes. 15...Reactions of Hexafluro- Technical Report cvclotriphosDhazene with Tert- and n-Butvl Lithium Reagents . PERFORMING ORG. REPORT NUMSER 7. AUTHOR•,) S

Two related lithium calixarene complexes, [p-tert-butylcalix[4]arene(OMe)(OH)2(OLi)](2).4MeCN and {p-tert-butylcalix[4]arene(OH)2(OLi)[OLi(NCMe)2]}(2).8MeCN, determined using synchrotron radiation.

PubMed

Lee, Darren S; Elsegood, Mark R J; Redshaw, Carl; Zhan, Shuzhong

2009-08-01

The crystal structures of acetonitrile solvates of two related lithium calixarene complexes have been determined by low-temperature single-crystal X-ray diffraction using synchrotron radiation. Bis(mu-5,11,17,23-tetra-tert-butyl-26,28-dihydroxy-25-methoxy-27-oxidocalix[4]arene)dilithium(I) acetonitrile tetrasolvate, [Li2(C45H57O4)2].4C2H3N or [p-tert-butylcalix[4]arene(OMe)(OH)2(OLi)](2).4MeCN, (I), crystallizes with the complex across a centre of symmetry and with four molecules of unbound acetonitrile of crystallization per complex. Tetraacetonitrilebis(mu-5,11,17,23-tetra-tert-butyl-26,28-dihydroxy-25,27-dioxidocalix[4]arene)tetralithium(I) acetonitrile octasolvate, [Li4(C44H54O4)2(C2H3N)4].8C2H3N or {p-tert-butylcalix[4]arene(OH)2(OLi)[OLi(NCMe)2]}(2).8MeCN, (II), also crystallizes with the complex lying across a centre of symmetry and contains eight molecules of unbound acetonitrile per complex plus four more directly bound to two of the lithium ions, two on each ion. The cores of both complexes are partially supported by O-H...O hydrogen bonds. The methoxy methyl groups in (I) prevent the binding of any more than two Li+ ions, while the corresponding two O-atom sites in (II) bind an extra Li(+) ion each, making four in total. The calixarene cone adopts an undistorted cone conformation in (I), but an elliptical one in (II).

Protective effect of simple phenols from extravirgin olive oil against lipid peroxidation in intestinal Caco-2 cells.

PubMed

Deiana, Monica; Corona, Giulia; Incani, Alessandra; Loru, Debora; Rosa, Antonella; Atzeri, Angela; Paola Melis, M; Assunta Dessì, M

2010-10-01

Complex polyphenols present in extravirgin olive oil are not directly absorbed, but undergo gastrointestinal biotransformation, increasing the relative amount of tyrosol (TYR) and hydroxytyrosol (HT) entering the small and large intestine. We investigated the capacity of TYR and HT to inhibit the insult of dietary lipid hydroperoxydes on the intestinal mucosa, using cultures of Caco-2, a cell line with enterocyte-like features, and studying the effect of tert-butyl hydroperoxide (TBH) treatment on specific cell membrane lipid targets. The effect of homovanillic alcohol (HVA), metabolite of HT in humans and detected as metabolite of HT in Caco-2 cells, was also evaluated. Exposure to TBH induced a significant increase of the level of MDA, the formation of fatty acid hydroperoxides and 7-ketocholesterol and the loss of α-tocopherol. Pretreatment with both HT and HVA protected Caco-2 cells from oxidative damage: there was no significant detection of oxidation products and the level of α-tocopherol was preserved. Noteworthy, TYR also exerted a protective action against fatty acids degradation. In vitro trials, where the simple phenols were tested during linoleic acid and cholesterol oxidation, gave evidence of a direct scavenging of peroxyl radicals and suggested a hydrogen atom-donating activity. Copyright © 2010 Elsevier Ltd. All rights reserved.

Heterobimetallic Dioxygen Activation

PubMed Central

York, John T.; Llobet, Antoni; Cramer, Christopher J.; Tolman, William B.

2008-01-01

Heterobimetallic CuPd and CuPt bis(μ-oxo) complexes have been prepared by the reaction of (PPh3)2MO2 (M = Pd, Pt) with LCu(I) precursors (L = β-diketiminate and di- and triamine ligands) and characterized by low-temperature UV-vis, resonance Raman, and 1H and 31P{1H} NMR spectroscopy in conjunction with DFT calculations. The complexes decompose upon warming to yield OPPh3, and in one case this was shown to occur by an intramolecular process through crossover experiments using double-labeling (oxo and phosphine). The reactivity of one of the complexes, LMe2Cu(μ-O)2Pt(PPh3)2 (LMe2 = β-diketiminate), with a variety of reagents including CO2, 2,4-di-tert-butylphenol, 2,4-di-tert-butylphenolate, [NH4][PF6], and dihydroanthracene, was compared to that of homometallic Pt2 and Cu2 counterparts. Unlike typical [Cu2(μ-O)2]2+ cores which have electrophilic oxo groups, the oxo groups in the [Cu(μ-O)2Pt]+ core behave as bases and nucleophiles, similar to previously described Pt2 compounds. In addition, however, the [Cu(μ-O)2Pt]+ core is capable of oxidatively coupling 2,4-di-tert-butylphenol and 2,4-di-tert-butylphenolate. Theoretical evaluation of the electron affinities, basicities, and H-atom transfer kinetics and thermodynamics of the Cu2 and CuM (M = Pd, Pt) cores showed that the latter are more basic and form stronger O-H bonds. PMID:17550254

40 CFR 180.536 - Triazamate; tolerances for residues.

Code of Federal Regulations, 2011 CFR

2011-07-01

...) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances... the combined residues of triazamate (RH-7988) ethyl(3-tert-butyl-1-dimethylcarbamoyl-1H-1,2,4-triazol...

40 CFR 180.536 - Triazamate; tolerances for residues.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) PESTICIDE PROGRAMS TOLERANCES AND EXEMPTIONS FOR PESTICIDE CHEMICAL RESIDUES IN FOOD Specific Tolerances... the combined residues of triazamate (RH-7988) ethyl(3-tert-butyl-1-dimethylcarbamoyl-1H-1,2,4-triazol...

Design and Control of Glycerol-tert-Butyl Alcohol Etherification Process

PubMed Central

Vlad, Elena; Bozga, Grigore

2012-01-01

Design, economics, and plantwide control of a glycerol-tert-butyl alcohol (TBA) etherification plant are presented. The reaction takes place in liquid phase, in a plug flow reactor, using Amberlyst 15 as a catalyst. The products' separation is achieved by two distillation columns where high-purity ethers are obtained and a section involving extractive distillation with 1,4-butanediol as solvent, which separates TBA from the TBA/water azeotrope. Details of design performed in AspenPlus and an economic evaluation of the process are given. Three plantwide control structures are examined using a mass balance model of the plant. The preferred control structure fixes the fresh glycerol flow rate and the ratio glycerol + monoether : TBA at reactor-inlet. The stability and robustness in the operation are checked by rigorous dynamic simulation in AspenDynamics. PMID:23365512

Aerobic biodegradation of tert-butyl alcohol (TBA) by psychro- and thermo-tolerant cultures derived from granular activated carbon (GAC).

PubMed

Reinauer, Kimberly M; Zhang, Yang; Yang, Xiaomin; Finneran, Kevin T

2008-04-01

Tert-butyl alcohol (TBA) is a metabolite of methyl tert-butyl ether and is itself possibly a fuel oxygenate. The goals of this study were to enrich and characterize TBA-degrading micro-organism(s) from a granular activated carbon (GAC) unit currently treating TBA. The results reported herein describe the first aerobic, TBA-degrading cultures derived from GAC. Strains KR1 and YZ1 were enriched from a GAC sample in a bicarbonate-buffered freshwater medium. TBA was degraded to 10% of the initial concentration (2-5 mM) within 5 days after initial inoculation and was continuously degraded within 1 day of each re-amendment. Resting cell suspensions mineralized 70 and 60% of the TBA within 24 h for KR1 and YZ1, respectively. Performance optimization with resting cells was conducted to investigate kinetics and the extent of TBA degradation as influenced by oxygen, pH and temperature. The most favorable temperature was 37 degrees C; however, TBA was degraded from 4 to 60 degrees C, indicating that the culture will sufficiently treat groundwater without heating. This is also the first report of psychrotolerant or thermotolerant TBA biodegradation. The pH range for TBA degradation ran from 5.0 to 9.0. Phylogenetic data using a partial 16S rRNA gene sequence (570 bases) suggest that the primary members of KR1 and YZ1 include uncharacterized organisms within the genera Hydrogenophaga, Caulobacter, and Pannonibacter.

Anaerobic degradation of a mixture of MtBE, EtBE, TBA, and benzene under different redox conditions.

PubMed

van der Waals, Marcelle J; Pijls, Charles; Sinke, Anja J C; Langenhoff, Alette A M; Smidt, Hauke; Gerritse, Jan

2018-04-01

The increasing use of biobased fuels and fuel additives can potentially change the typical fuel-related contamination in soil and groundwater. Anaerobic biotransformation of the biofuel additive ethyl tert-butyl ether (EtBE), as well as of methyl tert-butyl ether (MtBE), benzene, and tert-butyl alcohol (TBA, a possible oxygenate metabolite), was studied at an industrially contaminated site and in the laboratory. Analysis of groundwater samples indicated that in the field MtBE was degraded, yielding TBA as major product. In batch microcosms, MtBE was degraded under different conditions: unamended control, with medium without added electron acceptors, or with ferrihydrite or sulfate (with or without medium) as electron acceptor, respectively. Degradation of EtBE was not observed under any of these conditions tested. TBA was partially depleted in parallel with MtBE. Results of microcosm experiments with MtBE substrate analogues, i.e., syringate, vanillate, or ferulate, were in line with the hypothesis that the observed TBA degradation is a cometabolic process. Microcosms with ferulate, syringate, isopropanol, or diethyl ether showed EtBE depletion up to 86.5% of the initial concentration after 83 days. Benzene was degraded in the unamended controls, with medium without added electron acceptors and with ferrihydrite, sulfate, or chlorate as electron acceptor, respectively. In the presence of nitrate, benzene was only degraded after addition of an anaerobic benzene-degrading community. Nitrate and chlorate hindered MtBE, EtBE, and TBA degradation.

Ionic-liquid-mediated poly(dimethylsiloxane)- grafted carbon nanotube fiber prepared by the sol-gel technique for the head space solid-phase microextraction of methyl tert-butyl ether using GC.

PubMed

Vatani, Hossein; Yazdi, Ali Sarafraz

2014-01-01

A headspace solid-phase microextraction method was developed for the preconcentration and extraction of methyl tert-butyl ether. An ionic-liquid-mediated multiwalled carbon nanotube-poly(dimethylsiloxane) hybrid coating, which was prepared by covalent functionalization of multiwalled carbon nanotubes with hydroxyl-terminated poly(dimethylsiloxane) using the sol-gel technique, was used as solid-phase microextraction adsorbent. This innovative fiber exhibited a highly porous surface structure, high thermal stability (at least 320°C) and long lifespan (over 210 uses). Potential factors affecting the extraction efficiency were optimized. Under the optimum conditions, the method LOD (S/N = 3) was 0.007 ng/mL and the LOQ (S/N = 10) was 0.03 ng/mL. The calibration curve was linear in the range of 0.03-200 ng/mL. The RSDs for one fiber (repeatability, n = 5) at three different concentrations (0.05, 1, and 150 ng/mL) were 5.1, 4.2, and 4.6% and for the fibers obtained from different batches (reproducibility, n = 3) were 6.5, 5.9, and 6.3%, respectively. The developed method was successfully applied to the determination of methyl tert-butyl ether in different real water samples on three consecutive days. The relative recoveries for the spiked samples with 0.05, 1, and 150 ng/mL were between 94-104%. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sterilization of Bacillus pumilus spores using supercritical fluid carbon dioxide containing various modifier solutions.

PubMed

Shieh, Edison; Paszczynski, Andrzej; Wai, Chien M; Lang, Qingyong; Crawford, Ronald L

2009-03-01

Supercritical fluid carbon dioxide (SF-CO(2)) with small amounts of chemical modifier(s) provides a very effective sterilization technique that should be useful for destroying microorganism on heat-sensitive devices such as instruments flown on planetary-bound spacecraft. Under a moderate temperature (50 degrees C) and pressure (100 atm), spores of Bacillus pumilus strains ATCC 7061 and SAFR 032 can be effectively inactivated/eliminated from metal surfaces and small electronic devices in only 45 min using optimized modifier concentrations. Modifiers explored in this study included hydrogen peroxide (H(2)O(2)), tert-butyl hydroperoxide, formic acid, and Triton X-100. During sterilization procedure the modifiers were continuously added to SF-CO(2) in either methanol or water at controlled concentrations. The lowest effective concentrations were established for each modifier. Complete elimination of both types of B. pumilus endospores occurred with an optimal modifier addition of either or 10% methanol containing 12% H(2)O(2) or 12% tert-butyl hydroperoxide in SF-CO(2), or a mixture of 6% H(2)O(2) and 6% tert-butyl hydroperoxide. Using water as the carrier of SF-CO(2) modifier, the complete elimination of spores viability of both B. pumilus strains occurred with an addition of either 3.3% water containing 3% H(2)O(2), or 3.3% water containing 10% methanol and 0.5% formic acid, or 3.3% water containing 10% methanol, 1% formic acid and 2% H(2)O(2).

Effect of benzene and ethylbenzene on the transcription of methyl-tert-butyl ether degradation genes of Methylibium petroleiphilum PM1.

PubMed

Joshi, Geetika; Schmidt, Radomir; Scow, Kate M; Denison, Michael S; Hristova, Krassimira R

2016-09-01

Methyl-tert-butyl ether (MTBE) and its degradation by-product, tert-butyl alcohol (TBA), are widespread contaminants detected frequently in groundwater in California. Since MTBE was used as a fuel oxygenate for almost two decades, leaking underground fuel storage tanks are an important source of contamination. Gasoline components such as BTEX (benzene, toluene, ethylbenzene and xylenes) are often present in mixtures with MTBE and TBA. Investigations of interactions between BTEX and MTBE degradation have not yielded consistent trends, and the molecular mechanisms of BTEX compounds' impact on MTBE degradation are not well understood. We investigated trends in transcription of biodegradation genes in the MTBE-degrading bacterium, Methylibium petroleiphilum PM1 upon exposure to MTBE, TBA, ethylbenzene and benzene as individual compounds or in mixtures. We designed real-time quantitative PCR assays to target functional genes of strain PM1 and provide evidence for induction of genes mdpA (MTBE monooxygenase), mdpJ (TBA hydroxylase) and bmoA (benzene monooxygenase) in response to MTBE, TBA and benzene, respectively. Delayed induction of mdpA and mdpJ transcription occurred with mixtures of benzene and MTBE or TBA, respectively. bmoA transcription was similar in the presence of MTBE or TBA with benzene as in their absence. Our results also indicate that ethylbenzene, previously proposed as an inhibitor of MTBE degradation in some bacteria, inhibits transcription of mdpA, mdpJ and bmoAgenes in strain PM1.

Effect of benzene and ethylbenzene on the transcription of methyl-tert-butyl ether degradation genes of Methylibium petroleiphilum PM1

PubMed Central

Joshi, Geetika; Schmidt, Radomir; Scow, Kate M.; Denison, Michael S.; Hristova, Krassimira R.

2016-01-01

Methyl-tert-butyl ether (MTBE) and its degradation by-product, tert-butyl alcohol (TBA), are widespread contaminants detected frequently in groundwater in California. Since MTBE was used as a fuel oxygenate for almost two decades, leaking underground fuel storage tanks are an important source of contamination. Gasoline components such as BTEX (benzene, toluene, ethylbenzene and xylenes) are often present in mixtures with MTBE and TBA. Investigations of interactions between BTEX and MTBE degradation have not yielded consistent trends, and the molecular mechanisms of BTEX compounds’ impact on MTBE degradation are not well understood. We investigated trends in transcription of biodegradation genes in the MTBE-degrading bacterium, Methylibium petroleiphilum PM1 upon exposure to MTBE, TBA, ethylbenzene and benzene as individual compounds or in mixtures. We designed real-time quantitative PCR assays to target functional genes of strain PM1 and provide evidence for induction of genes mdpA (MTBE monooxygenase), mdpJ (TBA hydroxylase) and bmoA (benzene monooxygenase) in response to MTBE, TBA and benzene, respectively. Delayed induction of mdpA and mdpJ transcription occurred with mixtures of benzene and MTBE or TBA, respectively. bmoA transcription was similar in the presence of MTBE or TBA with benzene as in their absence. Our results also indicate that ethylbenzene, previously proposed as an inhibitor of MTBE degradation in some bacteria, inhibits transcription of mdpA, mdpJ and bmoAgenes in strain PM1. PMID:27450417

40 CFR 469.22 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Trichloroethane methylene chloride naphthalene 2 Nitrophenol phenol bis (2-ethylhexyl) phthalate...-butyl phthalate anthracene 1,2 Diphenylhydrazine isophorone butyl benzyl pthalate 1,1 Dichloroethylene 2...

40 CFR 469.22 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Trichloroethane methylene chloride naphthalene 2 Nitrophenol phenol bis (2-ethylhexyl) phthalate...-butyl phthalate anthracene 1,2 Diphenylhydrazine isophorone butyl benzyl pthalate 1,1 Dichloroethylene 2...

New phenolic grape skin products from Vitis vinifera cv. Pinot Noir.

PubMed

Kneknopoulos, Petros; Skouroumounis, George K; Hayasaka, Yoji; Taylor, Dennis K

2011-02-09

Anthocyanins and their related compounds were extracted from grape skins of Pinot noir, using 50% aqueous methanol, and purified by solid phase extraction chromatography using XAD-7 resin to obtain a pigment-rich fraction. This fraction was subjected to multilayer coil countercurrent chromatography (MLCCC) using a quaternary solvent system consisting of tert-butyl methyl ether/n-butanol/acetonitrile/water acidified with 0.01% trifluoroacetic acid (2:2:0.1-1.8:5) (v/v/v/v) in a step gradient elution to separate anthocyanin oligomers from grape anthocyanins. In the process of the characterization of the MLCCC fractions by electrospray mass spectrometry, two noncolored anthocyanin derivatives were found and characterized on the basis of their mass spectral data. As a result, these compounds have been tentatively identified as coupling products between both hydrated malvidin-3-glucoside and peonidin-3-glucoside, with 2-S-glutathionyl caffeoyl tartaric acid (GRP). It is therefore proposed that grape skins contain this new class of coupling product, and a possible chemical pathway for their formation is suggested.

One molecule of ionic liquid and tert-alcohol on a polystyrene-support as catalysts for efficient nucleophilic substitution including fluorination.

PubMed

Shinde, Sandip S; Patil, Sunil N

2014-12-07

The tert-alcohol and ionic liquid solvents in one molecule [mim-(t)OH][OMs] was immobilized on polystyrene and reported to be a highly efficient catalyst in aliphatic nucleophilic substitution using alkali metal salts. Herein, we investigated the catalytic activity of a new structurally modified polymer-supported tert-alcohol functionalized imidazolium salt catalyst in nucleophilic substitution of 2-(3-methanesulfonyloxypropyoxy)naphthalene as a model substrate with various metal nucleophiles. The tert-alcohol moiety of the ionic liquid with a hexyl chain distance from polystyrene had a better catalytic activity compared to the other resin which lacked an alkyl linker and tert-alcohol moiety. We found that the maximum [mim-(t)OH][OMs] loading had the best catalytic efficacy among the tested polystyrene-based ionic liquids (PSILs) in nucleophilic fluorination. The catalytic efficiency of the PS[him-(t)OH][OMs] as a phase transfer catalyst (PTC) was determined by carrying out various nucleophilic substitutions using the corresponding alkali metal salts from the third to sixth periodic in CH3CN or tert-BuOH media. The scope of this protocol with primary and secondary polar substrates containing many heteroatoms is also reported. This PS[him-(t)OH][OMs] catalyst not only enhances the reactivity of alkali metal salts and reduces the formation of by-products but also affords high yield with easy isolation.

Ferrocenyl-substituted dinuclear Cu(II) complex: Synthesis, spectroscopy, electrochemistry, DFT calculations and catecholase activity

NASA Astrophysics Data System (ADS)

Emirik, Mustafa; Karaoğlu, Kaan; Serbest, Kerim; Menteşe, Emre; Yilmaz, Ismail

2016-02-01

A new ferrocenyl-substituted heterocyclic hydrazide ligand and its Cu(II) complex were prepared. The DFT calculations were performed to determine the electronic and molecular structures of the title compounds. The electronic spectra were calculated by using time-dependent DFT method, and the transitions were correlated with the molecular orbitals of the compounds. The bands assignments of IR spectra were achieved in the light of the theoretical vibrational spectral data and total energy distribution values calculated at DFT/B3LYP/6-311++G(d,p) level. The redox behaviors of the ferrocene derivatives were investigated by cyclic voltammetry. The compounds show reversible redox couple assignable to Fc+/Fc couple. The copper(II) complex behaves as an effective catalyst towards oxidation of 3,5-di-tert-butylcatechol to its corresponding quinone derivative in DMF saturated with O2. The reaction follows Michaelis-Menten enzymatic reaction kinetics with turnover numbers 2.32 × 103.

40 CFR 463.33 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... BAT effluent limitations guidelines for bis(2-ethylhexyl) phthalate, di-n-butyl phthalate, and dimethyl phthalate are reserved. (b) The Agency has determined that, with the exception of bis(2-ethylhexyl) phthalate, di-n-butyl phthalate, and dimethyl phthalate, there are no toxic pollutants in treatable...

40 CFR 463.33 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... BAT effluent limitations guidelines for bis(2-ethylhexyl) phthalate, di-n-butyl phthalate, and dimethyl phthalate are reserved. (b) The Agency has determined that, with the exception of bis(2-ethylhexyl) phthalate, di-n-butyl phthalate, and dimethyl phthalate, there are no toxic pollutants in treatable...

Effect of antioxidants on the performance and emission characteristics of a diesel engine fuelled by waste cooking sunflower methyl ester

NASA Astrophysics Data System (ADS)

Reddy, V. Puneeth Kumar; Senthil Kumar, D.; Thirumalini, S.

2018-02-01

Biodiesel is a renewable, biodegradable fuel produced from vegetable oils and animal fats. Nonetheless, its extensive utilization is impeded by the auto-oxidation resulting in degradation of the fuel. Adding antioxidants to the biodiesel is a potential solution, but it might have an effect on the clean-burning characteristics of the fuel. This paper investigates the effect of antioxidants on the performance and emission characteristics of a diesel engine fuelled by the waste cooking sunflower methyl ester. The fuel samples tested include B10, B20, B30 and B40, among which B20 produced the best possible results. Antioxidants 2, 6-ditert-butyl-4-methylphenol (BHA) and 2(3)-tert-butyl-4-methoxy phenol (BHT) of two concentrations 1000 ppm, 2000 ppm were added to B20 to evaluate the effectiveness. B20BHA1000 had the best effect with an average decrease of 5.035%, 2.02% in brake specific fuel consumption (BSFC) and exhaust gas temperature (EGT) compared to B20. Regarding the emission characteristics it was observed that B20BHA1000 had produced an increase of 7.21%, 27.79% in NOx and smoke emissions and a decrease of 33.33% in HC emissions when compared to B20. On the whole, without any requirement of alteration in the diesel engines, B20 blends with antioxidant can be utilized as fuel.

46 CFR Appendix I to Part 150 - Exceptions to the Chart

Code of Federal Regulations, 2011 CFR

2011-10-01

... alcohol (20) tert-Butyl alcohol, Methanol mixtures Decyl alcohol (20) iso-Decyl alcohol (20) Diacetone... listed below have been determined to be dangerously reactive, based on either data obtained in the...

46 CFR Appendix I to Part 150 - Exceptions to the Chart

Code of Federal Regulations, 2010 CFR

2010-10-01

... alcohol (20) tert-Butyl alcohol, Methanol mixtures Decyl alcohol (20) iso-Decyl alcohol (20) Diacetone... listed below have been determined to be dangerously reactive, based on either data obtained in the...

Microwave enhanced electroanalysis of formulations: processes in micellar media at glassy carbon and at platinum electrodes.

PubMed

Ghanem, Mohamed A; Compton, Richard G; Coles, Barry A; Canals, Antonio; Marken, Frank

2005-10-01

The direct electroanalysis of complex formulations containing alpha-tocopherol (vitamin E) is possible in micellar solution and employing microwave-enhanced voltammetry. In the presence of microwave radiation substantial heating and current enhancement effects have been observed at 330 microm diameter glassy carbon electrodes placed into a micellar aqueous solution and both hydrophilic and highly hydrophobic redox systems are detected. For the water soluble Fe(CN)(6)(3-/4-) redox system in micellar aqueous solutions of 0.1 M NaCl and 0.1 M sodium dodecylsulfate (SDS) at low to intermediate microwave power, thermal effects and convection effects are observed. At higher microwave power, thermal cavitation is induced and dominates the mass transport at the electrode surface. For the micelle-soluble redox systems tert-butylferrocene and 2,5-di-tert-butyl-1,4-benzoquinone, strong and concentration dependent current responses are observed only in the presence of microwave radiation. For the oxidation of micelle-soluble alpha-tocopherol current responses at glassy carbon electrodes are affected by adsorption and desorption processes whereas at platinum electrodes, analytical limiting currents are obtained over a wide range of alpha-tocopherol concentrations. However, for the determination of alpha-tocopherol in a commercial formulation interference from proteins is observed at platinum electrodes and direct measurements are possible only over a limited concentration range and at glassy carbon electrodes.

Identification and characterization of N-tert-butoxycarbonyl-MDMA: a new MDMA precursor.

PubMed

Collins, Michael; Donnelly, Christopher; Cameron, Shane; Tahtouh, Mark; Salouros, Helen

2017-03-01

In September 2015, 80 litres of a viscous, light-red liquid, described as hair product, was seized by the Australian Border Force (ABF). Initial testing by ABF indicated that the liquid was the 3,4-methylenedioxymethamphetamine (MDMA) precursor chemical safrole and custody of the material was transferred to the Australian Federal Police (AFP) who coordinated all subsequent investigations. Initial gas chromatography-mass spectrometry (GC-MS) analysis by the AFP indicated that the material was not safrole and samples of the liquid were transferred to the National Measurement Institute Australia (NMIA) for identification. Using a combination of nuclear magnetic resonance spectroscopy (NMR), GC-MS, infrared spectroscopy, and synthesis, the unknown substance was identified as N-tert.-butoxycarbonyl-MDMA (t-BOC-MDMA). The substance was also converted in high yield to MDMA (aqueous HCl, 80 °C, 30 min). The possibility that the t-BOC-MDMA may act as a pro-drug following ingestion was explored by exposure to simulated gastric juice (pH 1.5) and monitored by NMR (37 °C) at various intervals. The majority of t-BOC-MDMA was converted to MDMA after 305 min, which suggested that this derivatized form might serve as a pro-drug in vivo. An investigation into the chemistry of potential pro-drugs showed that t-BOC derivatives of methamphetamine, pseudoephedrine and 4-methylmethcahtinone (mephedrone) could also be prepared using di-tert.-butyl dicarbonate. The appearance of t-BOC-derivatives on the drug market requires further monitoring. © 2016 Commonwealth of Australia. Drug Testing and Analysis © 2016 John Wiley & Sons, Ltd. © 2016 Commonwealth of Australia. Drug Testing and Analysis © 2016 John Wiley & Sons, Ltd.

40 CFR Appendix J to Part 122 - NPDES Permit Testing Requirements for Publicly Owned Treatment Works (§ 122.21(j))

Code of Federal Regulations, 2012 CFR

2012-07-01

...-ethylhexyl) phthalate 4-bromophenyl phenyl ether Butyl benzyl phthalate 2-chloronaphthalene 4-chlorophenyl phenyl ether Chrysene Di-n-butyl phthalate Di-n-octyl phthalate Dibenzo(a,h)anthracene 1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene 3,3-dichlorobenzidine Diethyl phthalate Dimethyl phthalate...

Di-iso-Butyl Phthalate MATERNAL AND FETAL DATA FROM THE LE GRAY RESEARCH TEAM FOR NCEA June 15 2016

EPA Science Inventory

this file contains the raw data on the effects of in utero administration of di-iso-butyl phthalate on maternal weight gain during dosing and the numbers of fetuses and fetal resorptions. The data have all been previously published, as described on the file metadata sheet.

21 CFR 177.1632 - Poly (phenyl-enetereph-thala-mide) resins.

Code of Federal Regulations, 2010 CFR

2010-04-01

...). Poly(oxyethylene) sorbitol monolaurate tetraoleate (CAS Reg. No. 71243-28-2). Poly(oxyethylene) sorbitol hexaoleate (CAS Reg. No. 57171-56-9). 4,4′-Butylidenebis (6-tert-butyl-m-cresol) (CAS Reg. No. 85...

Chemoenzymatic synthesis of statine side chain building blocks and application in the total synthesis of the cholesterol-lowering compound solistatin.

PubMed

Rieder, Oliver; Wolberg, Michael; Foegen, Silke E; Müller, Michael

2017-09-20

The synthesis and enzymatic reduction of several 6-substituted dioxohexanoates are presented. Two-step syntheses of tert-butyl 6-bromo-3,5-dioxohexanoate and the corresponding 6-hydroxy compound have been achieved in 89% and 59% yield, respectively. Regio- and enantioselective reduction of these diketones and of the 6-chloro derivative with alcohol dehydrogenase from Lactobacillus brevis (LBADH) gave the (5S)-5-hydroxy-3-oxo products with enantiomeric excesses of 91%, 98.4%, and >99.5%, respectively. Chain elongation of the reduction products by one carbon via cyanide addition, and by more than one carbon by Julia-Kocienski olefination, gave access to well-established statine side-chain building blocks. Application in the synthesis of the cholesterol-lowering natural compound solistatin is given. Copyright © 2017 Elsevier B.V. All rights reserved.

Second Moments (planar Moments) and Their Application in Spectroscopy

NASA Astrophysics Data System (ADS)

Bohn, Robert K.; Montgomery, John A., Jr.; Michels, H. Harvey; Byrd, Jason N.

2013-06-01

Second moments, also called planar moments (P_{ii} = Σ m_{i}^{} x_{i}^{2}), are the spectroscopic parameters used to determine substitution structures (r_{s}) ) by Kraitchman''s method from spectra of a molecule and its isotopologs. They are also useful for discussing other molecular structural properties. Just as bond lengths and angles are considered transferable among similar molecules, second moments of many common groups are also transferable. This paper discusses applications of second moments of methylene/methyl groups, singly or multiply, isopropyl/tert-butyl groups, phenyl groups, per{f}{l}uoro methylene/methyl groups, combinations of any of them, and planarity of molecules, the historically most common application of second moments. The inertial defect is Δ = (I_{c} - I_{a} - I_{b}) or -2P_{cc}. Some authors err by assuming each isotopolog provides three independent rotational constants, but in some cases they are not all independent. J. Kraitchman, Am. J. Phys. {21 (17), 1953.}

Catalytic Activity of μ-Carbido-Dimeric Iron(IV) Octapropylporphyrazinate in the 3,5,7,2',4'-Pentahydroxyflavone Oxidation Reaction with tert-Butyl Hydroperoxide

NASA Astrophysics Data System (ADS)

Tyurin, D. V.; Zaitseva, S. V.; Kudrik, E. V.

2018-05-01

It is found for the first time that μ-carbido-dimeric iron(IV) octapropylporphyrazinate displays catalytic activity in the oxidation reaction of natural flavonol morin with tert-butyl hydroperoxide, with the catalyst being stable under conditions of the reaction. The kinetics of this reaction are studied. It is shown the reaction proceeds via tentative formation of a complex between the catalyst and the oxidant, followed by O‒O bond homolytic cleavage. The kinetics of the reaction is described in the coordinates of the Michaelis-Menten equation. A linear dependence of the apparent reaction rate constant on the concentration of the catalyst is observed, testifying to its participation in the limiting reaction step. The equilibrium constants and rates of interaction are found. A mechanism is proposed for the reaction on the basis of the experimental data.

Protective effect of ganodermanondiol isolated from the Lingzhi mushroom against tert-butyl hydroperoxide-induced hepatotoxicity through Nrf2-mediated antioxidant enzymes.

PubMed

Li, Bin; Lee, Dong-Sung; Kang, Yue; Yao, Nai-Qi; An, Ren-Bo; Kim, Youn-Chul

2013-03-01

Ganodermanondiol, a biologically active compound, was isolated from the Lingzhi mushroom (Ganoderma lucidum). The present study examined the protective effects of ganodermanondiol against tert-butyl hydroperoxide (t-BHP)-induced hepatotoxicity. Ganodermanondiol protected human liver-derived HepG2 cells through nuclear factor-E2-related factor 2 (Nrf2) pathway-dependent heme oxygenase-1 expressions. Moreover, ganodermanondiol increased cellular glutathione levels and the expression of the glutamine-cysteine ligase gene in a dose-dependent manner. Furthermore, ganodermanondiol exposure enhanced the phosphorylation of adenosine monophosphate-activated protein kinase (AMPK) and its upstream kinase activators, LKB1 and Ca(2+)/calmodulin-dependent protein kinase-II (CaMKII). This study indicates that ganodermanondiol exhibits potent cytoprotective effects on t-BHP-induced hepatotoxicity in human liver-derived HepG2 cells, presumably through Nrf2-mediated antioxidant enzymes and AMPK. Copyright © 2012 Elsevier Ltd. All rights reserved.

Bis[μ-N-(tert-butyl­dimethyl­silyl)-N-(pyridin-2-ylmeth­yl)amido]­bis­[methyl­cobalt(II)

PubMed Central

Malassa, Astrid; Agthe, Christine; Görls, Helmar; Westerhausen, Matthias

2012-01-01

The green title complex, [Co2(CH3)2(C12H21N2Si)2], was obtained from bis­{[μ-N-tert-butyl­dimethyl­silyl-N-(pyridin-2-ylmeth­yl)amido]­chloridocobalt(II)} and methyl­lithium in diethyl ether at 195 K via a metathesis reaction. The dimeric cobalt(II) complex exhibits a crystallographic center of inversion in the middle of the Co2N2 ring (average Co—N = 2.050 Å). The CoII atom shows a distorted tetra­hedral coordination sphere. The exocyclic Co—N bond length to the pyridyl group shows a similar value of 2.045 (4) Å. The exocyclic methyl group has a rather long Co—C bond length of 2.019 (5) Å. PMID:22969464

Protein dynamics in organic media at varying water activity studied by molecular dynamics simulation.

PubMed

Wedberg, Rasmus; Abildskov, Jens; Peters, Günther H

2012-03-01

In nonaqueous enzymology, control of enzyme hydration is commonly approached by fixing the thermodynamic water activity of the medium. In this work, we present a strategy for evaluating the water activity in molecular dynamics simulations of proteins in water/organic solvent mixtures. The method relies on determining the water content of the bulk phase and uses a combination of Kirkwood-Buff theory and free energy calculations to determine corresponding activity coefficients. We apply the method in a molecular dynamics study of Candida antarctica lipase B in pure water and the organic solvents methanol, tert-butyl alcohol, methyl tert-butyl ether, and hexane, each mixture at five different water activities. It is shown that similar water activity yields similar enzyme hydration in the different solvents. However, both solvent and water activity are shown to have profound effects on enzyme structure and flexibility.

A comparative study of biodiesel production using methanol, ethanol, and tert-butyl methyl ether (MTBE) under supercritical conditions.

PubMed

Farobie, Obie; Matsumura, Yukihiko

2015-09-01

In this study, biodiesel production under supercritical conditions among methanol, ethanol, and tert-butyl methyl ether (MTBE) was compared in order to elucidate the differences in their reaction behavior. A continuous reactor was employed, and experiments were conducted at various reaction temperatures (270-400 °C) and reaction times (3-30 min) and at a fixed pressure of 20 MPa and an oil-to-reactant molar ratio of 1:40. The results showed that under the same reaction conditions, the supercritical methanol method provided the highest yield of biodiesel. At 350 °C and 20 MPa, canola oil was completely converted to biodiesel after 10, 30, and 30 min in the case of - supercritical methanol, ethanol, and MTBE, respectively. The reaction kinetics of biodiesel production was also compared for supercritical methanol, ethanol, and MTBE. Copyright © 2015 Elsevier Ltd. All rights reserved.

Protective effect of vanilloids against tert-butyl hydroperoxide-induced oxidative stress in vero cells culture.

PubMed

Rosa, Antonella; Atzeri, Angela; Deiana, Monica; Melis, M Paola; Incani, Alessandra; Corona, Giulia; Loru, Debora; Appendino, Giovanni; Dessì, M Assunta

2008-05-28

This study investigated the effect of synthetic capsiate, a simplified analogue of capsiate, and vanillyl alcohol on the oxidative stress induced by tert-butyl hydroperoxide (TBH) in a line of fibroblasts derived from monkey kidney (Vero cells). In response to the TBH-mediated oxidative stress, a reduction of the levels of total unsaturated fatty acids and cholesterol was observed, and a rise in the concentrations of conjugated dienes fatty acids hydroperoxides and 7-ketocholesterol. Pretreatment with both synthetic capsiate and vanillyl alcohol preserved Vero cells from oxidative damage and showed a remarkable protective effect on the reduction of the levels of total unsaturated fatty acids and cholesterol, inhibiting the increase of MDA, conjugated dienes fatty acids hydroperoxides, and 7-ketocholesterol. Both compounds were effective against peroxidation of cell membrane lipids induced by TBH, with synthetic capsiate essentially acting as a pro-drug of vanillyl alcohol, its hydrophilic hydrolytic derivative.

Preparation of Langmuir-Blodgett thin films of calix[6]arenes and p-tert butyl group effect on their gas sensing properties

NASA Astrophysics Data System (ADS)

Ozmen, Mustafa; Ozbek, Zikriye; Bayrakci, Mevlut; Ertul, Seref; Ersoz, Mustafa; Capan, Rifat

2015-12-01

Organic vapor sensing properties of Langmuir-Blodgett (LB) thin films of p-tert-butyl calix[6]arene and calix[6]arene, and their certain characterization are reported in this work. LB films of these calixarenes have been characterized by contact angle measurement, quartz crystal microbalance (QCM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). QCM system was used for the measurement of sensor response against chloroform, benzene, toluene and ethanol vapors. Forming of stable monolayers was observed at the water surface using surface pressure-area isotherm graph. The results indicate that good quality, uniform LB films can be prepared with a transfer ratio of over 0.95. Due to the adsorption of vapors into the LB film structures; they yield a response to all vapors as of large, fast, and reproducible.

Excellent deep-blue emitting materials based on anthracene derivatives for non-doped organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Wang, Zhiqiang; Liu, Wei; Xu, Chen; Ji, Baoming; Zheng, Caijun; Zhang, Xiaohong

2016-08-01

Two deep-blue emitting materials 2-tert-butyl-9,10-bis(3,5-diphenylphenyl)anthracene (An-1) and 2-tert-butyl-9,10-bis(3,5-diphenylbiphenyl-4‧-yl)anthracene (An-2) were successfully synthesized by the Pd-catalyzed Suzuki coupling reaction. Both of these compounds have high thermal stabilities and show strong deep-blue emission as solid-state film as well as in n-hexane solution. Two non-doped electroluminescent devices employing An-1 and An-2 as emitting layers were fabricated by vacuum vapor deposition. These devices exhibited highly efficient and stable deep-blue emission with high color purity. The CIE coordinate and maximum EQE of An-1 based device are 4.2% and (0.16, 0.06), respectively. Device based on An-2 achieved a maximum EQE of 4.0% and a CIE coordinate of (0.16, 0.10).

The application of silicalite-1/fly ash cenosphere (S/FAC) zeolite composite for the adsorption of methyl tert-butyl ether (MTBE).

PubMed

Lu, Jia; Xu, Fang; Wang, Deju; Huang, Jue; Cai, Weimin

2009-06-15

Silicalite-1/fly ash cenosphere (S/FAC) zeolite composite has been applied for batch adsorption of methyl tert-butyl ether (MTBE) from water systems. Here the key experimental conditions, including the ratio of initial MTBE concentration to the amount weight of S/FAC, adsorption time and temperature, have been discussed in detail. The results show that approximately 93-95% MTBE could be adsorbed with initial concentration of MTBE solution 1000 microg l(-1). The column flow-through experiments also prove the high capacity of S/FAC composite for MTBE removal. The distinct advantages of S/FAC zeolite composite as adsorbent lie in (1) enhanced adsorption rate and capacity based on hierarchical micro and meso/macroporosity of S/FAC; (2) more easily operation and recycling process by assembly of nano-sized silicalite-1 zeolite on FAC support.

Gabapentin-base synthesis and theoretical studies of biologically active compounds: N-cyclohexyl-3-oxo-2-(3-oxo-2-azaspiro[4.5] decan-2-yl)-3-arylpropanamides and N-(tert-butyl)-2-(3-oxo-2-azaspiro[4.5]decan-2-yl)-2-arylacetamide derivatives

NASA Astrophysics Data System (ADS)

Amirani Poor, Mahboobe; Darehkordi, Ali; Anary-Abbasinejad, Mohammad; Mohammadi, Marziyeh

2018-01-01

An intermolecular Ugi reaction of 2-(1-(aminomethyl)cyclohexyl)acetic acid (gabapentin) with glyoxal and cyclohexyl isocyanide or aromatic aldehyde and tertbutyl isocyanide under mild conditions in ethanol have been developed to produce two novel class of N-cyclohexyl-3-(aryl)-3-oxo-2-(3-oxo-2-azaspiro[4.5]decan-2-yl)propanamideins and N-(tert-butyl)-2-(3-oxo-2-azaspiro[4.5]decan-2-yl)-2-arylacetamide derivatives in good to excellent yields. This presents the first report for the intermolecular Ugi three component reaction of gabapentin, glyoxal, and an isocyanide. Also according to the theoretical studies the electron-donating groups increase the strength of intramolecular hydrogen bond and electron-withdrawing groups decrease the strength of intramolecular hydrogen bond.

Concentrations of phthalates and bisphenol A in Norwegian foods and beverages and estimated dietary exposure in adults.

PubMed

Sakhi, Amrit K; Lillegaard, Inger Therese L; Voorspoels, Stefan; Carlsen, Monica H; Løken, Elin B; Brantsæter, Anne L; Haugen, Margaretha; Meltzer, Helle M; Thomsen, Cathrine

2014-12-01

Phthalates and bisphenol A (BPA) are ubiquitous in our environment. These chemicals have been characterized as endocrine disruptors that can cause functional impairment of development and reproduction. Processed and packaged foods are among the major sources of human exposure to these chemicals. No previous report showing the levels of these chemicals in food items purchased in Norway is available. The aim of the present study was to determine the concentration of ten different phthalates and BPA in foods and beverages purchased on the Norwegian market and estimate the daily dietary exposure in the Norwegian adult population. Commonly consumed foods and beverages in Norway were purchased in a grocery store and analysed using gas- and liquid chromatography coupled with mass spectrometry. Daily dietary exposures to these chemicals in the Norwegian adult population were estimated using the latest National dietary survey, Norkost 3 (2010-2011). This study showed that phthalates and BPA are found in all foods and beverages that are common to consume in Norway. The detection frequency of phthalates in the food items varied from 11% for dicyclohexyl phthalate (DCHP) to 84% for di-iso-nonyl phthalate (DiNP), one of the substitutes for bis(2-ethylhexyl) phthalate (DEHP). BPA was found in 54% of the food items analysed. Among the different phthalates, the highest concentrations were found for DEHP and DiNP in the food items. Estimated dietary exposures were also equally high and dominated by DEHP and DiNP (400-500 ng/kg body weight (bw)/day), followed by di-iso-butyl phthalate (DiBP), di-n-butyl phthalate (DnBP), di-n-octyl phthalate (DnOP) and di-iso-decyl phthalate (DiDP) (30-40 ng/kg bw/day). Dimethyl phthalate (DMP), diethylphthalate (DEP) and DCHP had the lowest concentrations and the exposures were around 10-20 ng/kg bw/day. Estimated dietary exposure to BPA was 5 ng/kg bw/day. In general, levels of phthalates and BPA in foods and beverages from the Norwegian market are comparable to other countries worldwide. Grain and meat products were the major contributors of exposure to these chemicals in the Norwegian adult population. The estimated dietary exposures to these chemicals were considerably lower than their respective tolerable daily intake (TDI) values established by the European Food Safety Authority (EFSA). Copyright © 2014 Elsevier Ltd. All rights reserved.

Radical pathway in catecholase activity with zinc-based model complexes of compartmental ligands.

PubMed

Guha, Averi; Chattopadhyay, Tanmay; Paul, Nanda Dulal; Mukherjee, Madhuparna; Goswami, Somen; Mondal, Tapan Kumar; Zangrando, Ennio; Das, Debasis

2012-08-20

Four dinuclear and three mononuclear Zn(II) complexes of phenol-based compartmental ligands (HL(1)-HL(7)) have been synthesized with the aim to investigate the viability of a radical pathway in catecholase activity. The complexes have been characterized by routine physicochemical studies as well as X-ray single-crystal structure analysis: [Zn(2)(H(2)L(1))(OH)(H(2)O)(NO(3))](NO(3))(3) (1), [Zn(2)L(2)Cl(3)] (2), [Zn(2)L(3)Cl(3)] (3), [Zn(2)(L(4))(2)(CH(3)COO)(2)] (4), [Zn(HL(5))Cl(2)] (5), [Zn(HL(6))Cl(2)] (6), and [Zn(HL(7))Cl(2)] (7) [L(1)-L(3) and L(5)-L(7) = 2,6-bis(R-iminomethyl)-4-methylphenolato, where R= N-ethylpiperazine for L(1), R = 2-(N-ethyl)pyridine for L(2), R = N-ethylpyrrolidine for L(3), R = N-methylbenzene for L(5), R = 2-(N-methyl)thiophene for L(6), R = 2-(N-ethyl)thiophene for L(7), and L(4) = 2-formyl-4-methyl-6-N-methylbenzene-iminomethyl-phenolato]. Catecholase-like activity of the complexes has been investigated in methanol medium by UV-vis spectrophotometric study using 3,5-di-tert-butylcatechol as model substrate. All complexes are highly active in catalyzing the aerobic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ). Conversion of 3,5-DTBC to 3,5-DTBQ catalyzed by mononuclear complexes (5-7) is observed to proceed via formation of two enzyme-substrate adducts, ES1 and ES2, detected spectroscopically, a finding reported for the first time in any Zn(II) complex catalyzed oxidation of catechol. On the other hand, no such enzyme-substrate adduct has been identified, and 3,5-DTBC to 3,5-DTBQ conversion is observed to be catalyzed by the dinuclear complexes (1-4) very smoothly. EPR experiment suggests generation of radicals in the presence of 3,5-DTBC, and that finding has been strengthened by cyclic voltammetric study. Thus, it may be proposed that the radical pathway is probably responsible for conversion of 3,5-DTBC to 3,5-DTBQ promoted by complexes of redox-innocent Zn(II) ion. The ligand-centered radical generation has further been verified by density functional theory calculation.

Fish in Vitro Digestion: Influence of Fish Salting on the Extent of Lipolysis, Oxidation, and Other Reactions.

PubMed

Nieva-Echevarría, Bárbara; Goicoechea, Encarnación; Manzanos, María J; Guillén, María D

2017-02-01

A study of the various chemical reactions which take place during fish in vitro digestion and the potential effect of fish salting on their extent is addressed for the first time. Farmed European sea bass fillets, raw, brine-salted or dry-salted, were digested using a gastrointestinal in vitro model. Fish lipid extracts before and after digestion were analyzed by 1 H NMR, and the headspace composition of the digestates was investigated by SPME-GC/MS. During digestion, not only lipolysis, but also fish lipid oxidation took place. This latter was evidenced by the generation of conjugated dienes supported on chains having also hydroperoxy- and hydroxy-groups (primary oxidation compounds), by the increase of volatile secondary oxidation products, and by the decrease of the antioxidant 2,6-di-tert-butyl-hydroxytoluene (BHT). Likewise, esterification and Maillard-type reactions also occurred. Salting, and especially dry-salting, enhanced all these reactions, except for lipolysis, during digestion.

Bonding coordination requirements induce antiferromagnetic coupling between m-phenylene bridged o-iminosemiquinonato diradicals.

PubMed

Dei, Andrea; Gatteschi, Dante; Sangregorio, Claudio; Sorace, Lorenzo; Vaz, Maria G F

2003-03-10

Triply bridged bis-iminodioxolene dinuclear metal complexes of general formula M(2)(diox-diox)(3), with M = Co, Fe, have been synthesized using the bis-bidentate ligand N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine. These complexes were characterized by means of X-ray, HF-EPR, and magnetic measurements. X-ray structures clearly show that both complexes can be described as containing three bis-iminosemiquinonato ligands acting in a bis-bidentate manner toward tripositive metal ions. The magnetic data show that both of these complexes have singlet ground states. The observed experimental behavior indicates the existence of intraligand antiferromagnetic interactions between the three pairs of m-phenylene units linked iminosemiquinonato radicals (J = 21 cm(-)(1) for the cobalt complex and J = 11 cm(-)(1) for the iron one). It is here suggested that the conditions for the ferromagnetic coupling that is expected to characterize the free diradical ligand are no longer satisfied because of the severe torsional distortion induced by the metal coordination.

Metalorganic Vapor-Phase Epitaxy Growth Parameters for Two-Dimensional MoS2

NASA Astrophysics Data System (ADS)

Marx, M.; Grundmann, A.; Lin, Y.-R.; Andrzejewski, D.; Kümmell, T.; Bacher, G.; Heuken, M.; Kalisch, H.; Vescan, A.

2018-02-01

The influence of the main growth parameters on the growth mechanism and film formation processes during metalorganic vapor-phase epitaxy (MOVPE) of two-dimensional MoS2 on sapphire (0001) have been investigated. Deposition was performed using molybdenum hexacarbonyl and di- tert-butyl sulfide as metalorganic precursors in a horizontal hot-wall MOVPE reactor from AIXTRON. The structural properties of the MoS2 films were analyzed by atomic force microscopy, scanning electron microscopy, and Raman spectroscopy. It was found that a substrate prebake step prior to growth reduced the nucleation density of the polycrystalline film. Simultaneously, the size of the MoS2 domains increased and the formation of parasitic carbonaceous film was suppressed. Additionally, the influence of growth parameters such as reactor pressure and surface temperature is discussed. An upper limit for these parameters was found, beyond which strong parasitic deposition or incorporation of carbon into MoS2 took place. This carbon contamination became significant at reactor pressure above 100 hPa and temperature above 900°C.

Polymer concrete composites for the production of high strength pipe and linings in high temperature corrosive environments

DOEpatents

Zeldin, A.; Carciello, N.; Fontana, J.; Kukacka, L.

High temperature corrosive resistant, non-aqueous polymer concrete composites are described. They comprise about 12 to 20% by weight of a water-insoluble polymer binder polymerized in situ from a liquid monomer mixture consisting essentially of about 40 to 70% by weight of styrene, about 25 to 45% by weight acrylonitrile and about 2.5 to 7.5% by weight acrylamide or methacrylamide and about 1 to 10% by weight of a crosslinking agent. This agent is selected from the group consisting of trimethylolpropane trimethacrylate and divinyl benzene; and about 80 to 88% by weight of an inert inorganic filler system containing silica sand and portland cement, and optionally Fe/sub 2/O/sub 3/ or carbon black or mica. A free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, other organic peroxides and combinations thereof to initiate crosspolymerization of the monomer mixture in the presence of said inorganic filler.

Potential hepatoprotective effects of new Cuban natural products in rat hepatocytes culture.

PubMed

Rodeiro, I; Donato, M T; Martínez, I; Hernández, I; Garrido, G; González-Lavaut, J A; Menéndez, R; Laguna, A; Castell, J V; Gómez-Lechón, M J

2008-08-01

The protective effects of five Cuban natural products (Mangifera indica L. (MSBE), Erythroxylum minutifolium, Erythroxylum confusum, Thalassia testudinum and Dictyota pinnatifida extracts and mangiferin) on the oxidative damage induced by model toxicants in rat hepatocyte cultures were studied. Cells were pre-incubated with the natural products (5-200 microg/mL) for 24 h. Then hepatotoxins (tert-butyl hydroperoxide, ethanol, carbon tetrachloride and lipopolysaccharide) were individually added and post-incubated for another 24 h. After treatments, cell viability was determined using the MTT assay. Mangiferin and MSBE exhibited the highest cytoprotective potential (EC50 between 50 and 125 microg/mL), followed by T. testudinum and Erythroxylum extracts, whereas no significant protective effects was produced by Dictyota extract treatment. Antioxidant properties of the natural products against lipid peroxidation and GSH depletion induced by tert-butyl hydroperoxide were then investigated. The results show that at 36 h pre-treatment of cells with mangiferin or MSBE, concentrations of T. testudinum and Erythroxylum extracts ranging from 25 to 100 microg/mL significantly inhibited lipid peroxidation induced by tert-butyl hydroperoxide (100 and 250 microM) and increased the GSH levels reduced by the toxicant. D. pinnatifida inhibited lipid peroxidation, but did not preserve GSH levels. In conclusion, MSBE, E. minutifolium, E. confusum and T. testudinum extracts and mangiferin showed hepatoprotective activity against induced damage in all the experimental series, where mangiferin and the extracts of MSBE and T. testudinum were the best candidates to inhibit "in vitro" damage to rat hepatocytes. This hepatoprotective effect found could be associated with the antioxidant properties observed for the products.

Poly(Acrylic Acid-b-Styrene) Amphiphilic Multiblock Copolymers as Building Blocks for the Assembly of Discrete Nanoparticles

PubMed Central

Greene, Anna C.; Zhu, Jiahua; Pochan, Darrin J.; Jia, Xinqiao; Kiick, Kristi L.

2011-01-01

In order to expand the utility of current polymeric micellar systems, we have developed amphiphilic multiblock copolymers containing alternating blocks of poly(acrylic acid) and poly(styrene). Heterotelechelic poly(tert-butyl acrylate-b-styrene) diblock copolymers containing an α-alkyne and an ω-azide were synthesized by atom transfer radical polymerization (ATRP), allowing control over the molecular weight while maintaining narrow polydispersity indices. The multiblock copolymers were constructed by copper-catalyzed azide-alkyne cycloaddition of azide-alkyne end functional diblock copolymers which were then characterized by 1H NMR, FT-IR and SEC. The tert-butyl moieties of the poly(tert-butyl acrylate-b-styrene) multiblock copolymers were easily removed to form the poly(acrylic acid-b-styrene) multiblock copolymer ((PAA-PS)9), which contained up to 9 diblock repeats. The amphiphilic multiblock (PAA-PS)9 (Mn = 73.3 kg/mol) was self-assembled by dissolution into tetrahydrofuran and extensive dialysis against deionized water for 4 days. The critical micelle concentration (CMC) for (PAA-PS)9 was determined by fluorescence spectroscopy using pyrene as a fluorescent probe and was found to be very low at 2 × 10-4 mg/mL. The (PAA-PS)9 multiblock was also analyzed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The hydrodynamic diameter of the particles was found to be 11 nm. Discrete spherical particles were observed by TEM with an average particle diameter of 14 nm. The poly(acrylic acid) periphery of the spherical particles should allow for future conjugation of biomolecules. PMID:21552373

FENTON-DRIVEN CHEMICAL REGENERATION OF MTBE-SPENT GAC

EPA Science Inventory

Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was chemically regenerated utilizing the Fenton mechanism. Two successive GAC regeneration cycles were performed involving iterative adsorption and oxidation processes: MTBE was adsorbed to the GAC, oxidized, r...

DI(N-BUTYL) PHTHALATE AND DIETHYLHEXYL PHTHALATE IN COMBINATION ALTER SEXUAL DIFFERENTIATION IN A CUMULATIVE MANNER AS A RESULT OF DEPRESSED FETAL TESTOSTERONE PRODUCTION AND INSL3 GENE EXPRESSION IN MALE RATS

EPA Science Inventory

Plasticizers di(n-butyl) phthalate (DBP) and diehtylhexyl phthalate (DEHP) have similar modes of action: in utero exposure reduces testosterone (T) production in fetal male rats, inhibits reproductive tract differentiation, and induces reproductive organ malformations. In utero e...

An ion-pair principle for enantioseparations of basic analytes by nonaqueous capillary electrophoresis using the di-n-butyl L-tartrate-boric acid complex as chiral selector.

PubMed

Wang, Li-Juan; Liu, Xiu-Feng; Lu, Qie-Nan; Yang, Geng-Liang; Chen, Xing-Guo

2013-04-05

A chiral recognition mechanism of ion-pair principle has been proposed in this study. It rationalized the enantioseparations of some basic analytes using the complex of di-n-butyl l-tartrate and boric acid as the chiral selector in methanolic background electrolytes (BGEs) by nonaqueous capillary electrophoresis (NACE). An approach of mass spectrometer (MS) directly confirmed that triethylamine promoted the formation of negatively charged di-n-butyl l-tartrate-boric acid complex chiral counter ion with a complex ratio of 2:1. And the negatively charged counter ion was the real chiral selector in the ion-pair principle enantioseparations. It was assumed that triethylamine should play its role by adjusting the apparent acidity (pH*) of the running buffer to a higher value. Consequently, the effects of various basic electrolytes including inorganic and organic ones on the enantioseparations in NACE were investigated. The results showed that most of the basic electrolytes tested were favorable for the enantioseparations of basic analytes using di-n-butyl l-tartrate-boric acid complex as the chiral ion-pair selector. Copyright © 2013 Elsevier B.V. All rights reserved.

Degradation of organic pollutants by methane grown microbial consortia.

PubMed

Hesselsoe, Martin; Boysen, Susanne; Iversen, Niels; Jørgensen, Lars; Murrell, J Colin; McDonald, Ian; Radajewski, Stefan; Thestrup, Helle; Roslev, Peter

2005-10-01

Microbial consortia were enriched from various environmental samples with methane as the sole carbon and energy source. Selected consortia that showed a capacity for co-oxidation of naphthalene were screened for their ability to degrade methyl-tert-butyl-ether (MTBE), phthalic acid esters (PAE), benzene, xylene and toluene (BTX). MTBE was not removed within 24 h by any of the consortia examined. One consortium enriched from activated sludge ("AAE-A2"), degraded PAE, including (butyl-benzyl)phthalate (BBP), and di-(butyl)phthalate (DBP). PAE have not previously been described as substrates for methanotrophic consortia. The apparent Km and Vmax for DBP degradation by AAE-A2 at 20 degrees C was 3.1 +/- 1.2 mg l(-1) and 8.7 +/- 1.1 mg DBP (g protein x h)(-1), respectively. AAE-A2 also showed fast degradation of BTX (230 +/- 30 nmol benzene (mg protein x h)(-1) at 20 degrees C). Additionally, AAE-A2 degraded benzene continuously for 2 weeks. In contrast, a pure culture of the methanotroph Methylosinus trichosporium OB3b ceased benzene degradation after only 2 days. Experiments with methane mono-oxygenase inhibitors or competitive substrates suggested that BTX degradation was carried out by methane-oxidizing bacteria in the consortium, whereas the degradation of PAE was carried out by non-methanotrophic bacteria co-existing with methanotrophs. The composition of the consortium (AAE-A2) based on polar lipid fatty acid (PLFA) profiles showed dominance of type II methanotrophs (83-92% of biomass). Phylogeny based on a 16S-rRNA gene clone library revealed that the dominating methanotrophs belonged to Methylosinus/Methylocystis spp. and that members of at least 4 different non-methanotrophic genera were present (Pseudomonas, Flavobacterium, Janthinobacterium and Rubivivax).

Impact of Storage Conditions on the Stability of Predominant Phenolic Constituents and Antioxidant Activity of Dried Piper betle Extracts.

PubMed

Ali, Ameena; Chong, Chien Hwa; Mah, Siau Hui; Abdullah, Luqman Chuah; Choong, Thomas Shean Yaw; Chua, Bee Lin

2018-02-23

The phenolic constituents in Piper betle are well known for their antioxidant potential; however, current literature has very little information on their stability under the influence of storage factors. Present study evaluated the stability of total phenolic content (TPC) and antioxidant activity together with individual phenolic constituents (hydroxychavicol, eugenol, isoeugenol and allylpyrocatechol 3,4-diacetate) present in dried Piper betle 's extract under different storage temperature of 5 and 25 °C with and without light for a period of six months. Both light and temperature significantly influenced TPC and its corresponding antioxidant activity over time. More than 95% TPC and antioxidant activity was retained at 5 °C in dark condition after 180 days of storage. Hydroxychavicol demonstrated the best stability with no degradation while eugenol and isoeugenol displayed moderate stability in low temperature (5 °C) and dark conditions. 4-allyl-1,2-diacetoxybenzene was the only compound that underwent complete degradation. A new compound, 2,4-di- tert -butylphenol, was detected after five weeks of storage only in the extracts exposed to light. Both zero-order and first-order kinetic models were adopted to describe the degradation kinetics of the extract's antioxidant activity. Zero-order displayed better fit with higher correlation coefficients ( R ² = 0.9046) and the half-life was determined as 62 days for the optimised storage conditions (5 °C in dark conditions).

Separation and purification of polyphenols from red wine extracts using high speed counter current chromatography.

PubMed

Li, Yuanyuan; Li, Lingxi; Cui, Yan; Zhang, Shuting; Sun, Baoshan

2017-06-01

Polyphenols are important compounds of red wine owing to their contribution to sensory properties and antioxidant activities. In this study, high-speed counter-current chromatography (HSCCC) coupled with semi-preparative HPLC was used for large-scale separation and purification of polyphenols from red wine extracts. With the solvent system of hexane-ethyl acetate-water (1-50-50), various oligomeric procyanidins including monomer catechin, epicatechin, dimers B1, B2; phenolic acids including coutaric acid, caftaric acid and other type of polyphenols were largely separated within 370min and most of these compounds presented high yields (0.97mg to 13.79mg) with high purity (90.34% to 98.91%) after the semi-preparative HPLC isolation. Using the solvent system of Methyl tert-Butyl Ether (MTBE) - n-butyl alcohol- acetonitrile-water (1-40-1-50, acidified with 0.01% trifluoroacetic acid (TFA)) by one-step HSCCC of 100mg of the red wine extracts, the major anthocyanins, i.e., malvidin-3-O-glucoside, delphinidin-3-O-glucoside and peonidin-3-O-glucoside, as well as two polymeric proanthocyanidin fractions were successfully separated one another within 320min. The yields of malvidin-3-O-glucoside, delphinidin-3-O-glucoside and peonidin-3-O-glucoside were 12.12mg, 1.78mg and 11.57mg with the purity of 92.74%, 91.03% and 91.21%, respectively. Thiolysis-UPLC analysis indicated that the two polymeric proanthocyanidin fractions presented high purity, with mean degree of polymerization of 7.66±0.12 and 6.20±0.09, respectively. The further experiments on the antioxidant activities by DPPH radical test, FRAP assay and ABTS method showed that all of the isolated procyandins and anthocyanins and the two polymeric proanthocyanidin fractions, with exception of phenolic acids possessed much greater antioxidant activities compared to standard Trolox andl-ascorbic acid (2-14 times). Copyright © 2017 Elsevier B.V. All rights reserved.

Fenton-Driven Regeneration of MTBE-spent Granular Activated Carbon

EPA Science Inventory

Fenton-driven regeneration of Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) involves the combined, synergistic use of two treatment technologies: adsorption of organic chemicals onto activated carbon and Fenton-driven oxidation regeneration of the spent-GAC...

Determination Co 2+ in vitamin B 12 based on enhancement of 2-(4-substituted-phenyl)-4,5-di(2-furyl) imidazole and H 2O 2 chemiluminescence reaction

NASA Astrophysics Data System (ADS)

Han, Lu; Zhang, Yumin; Kang, Jing; Tang, Jieli; Zhang, Yihua

2011-11-01

In this paper, three kinds of imidazole derivatives, 2-(4-methylphenyl)-4,5-di(2-furyl) imidazole (MDFI), 2-(4-nitrophenyl)-4,5-di(2-furyl) imidazole (NDFI), and 2-(4-tert-butylphenyl)-4,5-di(2-furyl) imidazole (t-BDFI) were synthesized. In an alkaline medium, the chemiluminescence (CL) reaction of imidazole derivatives with H 2O 2 has been investigated. It was also found that MDFI/H 2O 2 and t-BDFI/H 2O 2 systems gave strong CL. When Co 2+ was added into the two CL systems, the CL intensity was remarkably enhanced. In the optimum conditions, the CL intensity is linearly related to the logarithm of concentration of Co 2+. The linear ranges are 5 × 10 -9-2.5 × 10 -7 mol/L for MDFI/H 2O 2 system and 5 × 10 -9-2.5 × 10 -7 mol/L for t-BDFI/H 2O 2 system, and the corresponding detection limits are 1.2 × 10 -9 mol/L and 1.1 × 10 -9 mol/L, respectively. The method was applied to the determination of Co 2+ in vitamin B 12 injection. Furthermore, the CL mechanism was also discussed.

Urinary concentrations of phthalates and phenols in a population of Spanish pregnant women and children.

PubMed

Casas, Lidia; Fernández, Mariana F; Llop, Sabrina; Guxens, Mònica; Ballester, Ferran; Olea, Nicolás; Irurzun, Mikel Basterrechea; Rodríguez, Loreto Santa Marina; Riaño, Isolina; Tardón, Adonina; Vrijheid, Martine; Calafat, Antonia M; Sunyer, Jordi

2011-07-01

Phthalate and phenol exposure is prevalent among the general population and of potential concern for pregnant women and children because of their suspected susceptibility to endocrine effects. To evaluate the extent of exposure to several phthalates and phenols in a sample of Spanish pregnant women - according to their individual characteristics (age, social class, education, and body mass index) - and children who participated in the INMA - Infancia y Medio Ambiente (Environment and Childhood) project. One spot urine sample was taken during the third trimester of pregnancy from 120 pregnant women and from 30 4-year old children belonging to 5 Spanish birth cohorts, and analyzed for 11 phthalate metabolites and 9 phenols. Three metabolites of di(2-ethylhexyl) phthalate, mono-2-ethyl-5-carboxypentyl phthalate, mono-2-ethyl-5-hydroxyhexyl phthalate, and mono-2-ethyl-5-oxohexyl phthalate; two metabolites of dibutyl phthalates, mono-isobutyl phthalate and mono-n-butyl phthalate; monoethyl phthalate (MEP), the main metabolite of diethyl phthalate; and two phenols, methyl paraben (M-PB) and 2,5-dichlorophenol were detected in the urine samples of all women. The highest urinary concentrations were for MEP and M-PB. Urinary concentrations of all phthalate metabolites and of 2,4-dichlorophenol, 2,5-dichlorophenol, and bisphenol A were lower in the pregnant women than in the children. Among women, a positive relationship with social class and education was shown for most of the phthalate metabolites and phenols. Almost all phthalate metabolites varied by region even after adjusting for social class and education. Phthalate and phenol exposures are prevalent in a group of pregnant women and young children, two susceptible populations, and these exposures might be positively related to social class. Copyright © 2011 Elsevier Ltd. All rights reserved.

Reactivity of superoxide radical anion and hydroperoxyl radical with alpha-phenyl-N-tert-butylnitrone (PBN) derivatives.

PubMed

Durand, Grégory; Choteau, Fanny; Pucci, Bernard; Villamena, Frederick A

2008-12-04

Nitrones have exhibited pharmacological activity against radical-mediated pathophysiological conditions and as analytical reagents for the identification of transient radical species by electron paramagnetic resonance (EPR) spectroscopy. In this work, competitive spin trapping, stopped-flow kinetics, and density functional theory (DFT) were employed to assess and predict the reactivity of O(2)(*-) and HO(2)(*) with various para-substituted alpha-phenyl-N-tert-butylnitrone (PBN) spin traps. Rate constants of O(2)(*-) trapping by nitrones were determined using competitive UV-vis stopped-flow method with phenol red (PR) as probe, while HO(2)(*) trapping rate constants were calculated using competition kinetics with 5,5-dimethylpyrroline N-oxide (DMPO) by employing EPR spectroscopy. The effects of the para substitution on the charge density of the nitronyl-carbon and on the free energies of nitrone reactivity with O(2)(*-) and HO(2)(*) were computationally rationalized at the PCM/B3LYP/6-31+G(d,p)//B3LYP/6-31G(d) level of theory. Theoretical and experimental data show that the rate of O(2)(*-) addition to PBN derivatives is not affected by the polar effect of the substituents. However, the reactivity of HO(2)(*) follows the Hammett equation and is increased as the substituent becomes more electron withdrawing. This supports the conclusion that the nature of HO(2)(*) addition to PBN derivatives is electrophilic, while the addition of O(2)(*-) to PBN-type compounds is only weakly electrophilic.

Antioxidant properties of di-tert-butylhydroxylated flavonoids.

PubMed

Lebeau, J; Furman, C; Bernier, J L; Duriez, P; Teissier, E; Cotelle, N

2000-11-01

Epidemiological evidence suggests an inverse relationship between dietary intake of flavonoids and cardiovascular risk. The biological activities of flavonoids are related to their antioxidative effects, but they also can be mutagenic, due to the prooxidant activity of the catechol pattern. To prevent these problems, we synthesized new flavonoids where one or two di-tert-butylhydroxyphenyl (DBHP) groups replaced catechol moiety at position 2 of the benzopyrane heterocycle. Two DBHP moieties can also be arranged in an arylidene structure or one DBHP fixed on a chalcone structure. Position 7 on the flavone and arylidene or position 4 on the chalcone was substituted by H, OCH(3), or OH. New structures were compared with quercetin and BHT in an LDL oxidation system induced by Cu(II) ions. Arylidenes and chalcones had the best activities (ED(50) = 0.86 and 0.21) compared with vitamin E, BHT, and quercetin (ED(50) = 10.0, 7. 4, and 2.3 microM). Activity towards stable free radical 1, 1-diphenyl-2-picryl-hydrazyl (DPPH) was measured by log Z and ECR(50) parameters. Synthesized flavones proved to be poor DPPH radical scavengers, the activity increasing with the number of DBHP units. In contrast, arylidenes and chalcones were stronger DPPH radical scavengers (log Z > 3, 0.3 < ECR(50) < 2.12) than BHT (log Z = 0.75, ECR(50) = 12.56) or quercetin (log Z = 2.76, ECR(50) = 0.43). Unlike quercetin, synthesized compounds neither chelated nor reduced copper, proving that these new flavonoids had no prooxidant activity in vitro.

Açaí (Euterpe oleraceae Mart.) berry extract exerts neuroprotective effects against β-amyloid exposure in vitro.

PubMed

Wong, Daphne Yiu San; Musgrave, Ian Francis; Harvey, Benjamin Scott; Smid, Scott Darryl

2013-11-27

The native South American palm açaí berry (Euterpe oleraceae Mart.) has high polyphenolic and antioxidant levels. This study examined whether açaí berry extract afforded protection against β-amyloid (Aβ)-mediated loss of cell viability and oxidative stress associated with anti-fibrillar effects. PC12 cells were exposed to either Aβ1-42, Aβ25-35 or tert butyl hydroperoxide (t-BHP), alone or in the presence of açaí extract (0.5-50μg/ml). Thioflavin T (ThT) binding assay and transmission electron microscopy were used to determine effects of açaí extract on Aβ1-42 fibril morphology and compared to açaí phenolics gallic acid, cyanidin rutinoside and cyanidin glucoside. Exposure to Aβ1-42, Aβ25-35 or t-BHP decreased PC12 cell viability. Pretreatment with açaí extract significantly improved cell viability following Aβ1-42 exposure, however Aβ25-35 or t-BHP-mediated viability loss was unaltered. Açaí extract inhibited ThT fluorescence and disrupted Aβ1-42 fibril and aggregate morphology. In comparison with other phenolics, açaí was most effective at inhibiting Aβ1-42 aggregation. Inhibition of β-amyloid aggregation may underlie a neuroprotective effect of açaí. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Isolation of strawberry anthocyanins using high-speed counter-current chromatography and the copigmentation with catechin or epicatechin by high pressure processing.

PubMed

Zou, Hui; Ma, Yan; Xu, Zhenzhen; Liao, Xiaojun; Chen, Ailiang; Yang, Shuming

2018-05-01

Three anthocyanins were isolated from strawberry extract by high-speed counter-current chromatography, using a biphasic mixture of tert-butyl methyl ether, n-butanol, acetonitrile, water and trifluoroacetic acid (2.5:2.0:2.5:5.0:1.0%). The anthocyanins were identified as pelargonidin-3-rutinoside, cyanidin-3-glucoside and pelargonidin-3-glucoside with purity of 95.6%, 96.2% and 99.3% respectively. Additionally, the copigmentation reaction rates between pelargonidin-3-glucoside and phenolic acids (catechin or epicatechin) at pH 1.5 and 3.6, pressure 0.1 and 500 MPa, and temperature 60 °C were calculated. The absorbance of pelargonidin-3-glucoside at pH 3.6, with high quantity of phenolic acids was significantly increased by high pressure. The complex of pelargonidin-3-glucoside/catechin has a binding energy of 78.64 kJ/mol at pH 3.6, and 39.13 kJ/mol at pH 1.5; pelargonidin-3-glucoside/epicatechin has a binding energy of 75.34 kJ/mol at pH 1.5 and 54.47 kJ/mol at pH 3.6. The hydrogen bond and van der Waals interaction were the main forces contributing to the structures of complex. Copyright © 2017 Elsevier Ltd. All rights reserved.

In Silico Study of Chromatographic Lipophilicity Parameters of 3-(4-Substituted Benzyl)-5-Phenylhydantoins.

PubMed

Sekulic, Tatjana Djakovic; Keleman, Svetlana; Tot, Kristina; Tot, Jadranka; Trisovic, Nemanja; Uscumlic, Gordana

2016-01-01

New synthesized compounds, particularly those with biological activity, are potential drug candidates. This article describes experimental studies performed to estimate lipophilicity parameters of new 3-(4-substituted benzyl)-5-phenylhydantoins. Lipophilicity, as one of the most important molecular characteristics for the activity, was determined using the reversed-phase liquid chromatography (RP-18 stationary phase and methanol-water mobile phase). Molecular structures were used to generate in silico data which were used to estimate pharmacokinetic properties of the investigated compounds. The results show that generally, the investigated compounds attain good bioavailability properties. A more detailed analysis shows that the presence of a nitro, methoxy and tert-butyl group in the molecule is indicated as unfavorable for the oral bioavailability of hydantoins. Multivariate exploratory analysis was used in order to visualize grouping patterns among molecular descriptors as well as among the investigated compounds. Molecular docking study performed for two hydantoins with the highest bioavailability scores shows high binding affinity to tyrosine kinase receptor IGF-1R. The results achieved can be useful as a template for future development and further derivation or modification to obtain more potent and selective antitumor agents.

Imaging dynamic fingerprints of competing E2 and SN2 reactions.

PubMed

Carrascosa, Eduardo; Meyer, Jennifer; Zhang, Jiaxu; Stei, Martin; Michaelsen, Tim; Hase, William L; Yang, Li; Wester, Roland

2017-06-21

The competition between bimolecular nucleophilic substitution and base-induced elimination is of fundamental importance for the synthesis of pure samples in organic chemistry. Many factors that influence this competition have been identified over the years, but the underlying atomistic dynamics have remained difficult to observe. We present product velocity distributions for a series of reactive collisions of the type X -  + RY with X and Y denoting the halogen atoms fluorine, chlorine and iodine. By increasing the size of the residue R from methyl to tert-butyl in several steps, we find that the dynamics drastically change from backward to dominant forward scattering of the leaving ion relative to the reactant RY velocity. This characteristic fingerprint is also confirmed by direct dynamics simulations for ethyl as residue and attributed to the dynamics of elimination reactions. This work opens the door to a detailed atomistic understanding of transformation reactions in even larger systems.The competition between chemical reactions critically affects our natural environment and the synthesis of new materials. Here, the authors present an approach to directly image distinct fingerprints of essential organic reactions and monitor their competition as a function of steric substitution.

40 CFR 469.22 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... trichloroethylene 2 Chlorophenol 2,4 Dichlorophenol 4 Nitrophenol pentachlorophenol di-n-butyl phthalate anthracene 1,2 Diphenylhydrazine isophorone butyl benzyl pthalate 1,1 Dichloroethylene 2,4,6 Trichlorophenol...

40 CFR 469.22 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... trichloroethylene 2 Chlorophenol 2,4 Dichlorophenol 4 Nitrophenol pentachlorophenol di-n-butyl phthalate anthracene 1,2 Diphenylhydrazine isophorone butyl benzyl pthalate 1,1 Dichloroethylene 2,4,6 Trichlorophenol...

Investigation of steric influences on hydrogen-bonding motifs in cyclic ureas by using X-ray, neutron, and computational methods.

PubMed

McCormick, Laura J; McDonnell-Worth, Ciaran; Platts, James A; Edwards, Alison J; Turner, David R

2013-11-01

A series of urea-derived heterocycles, 5N-substituted hexahydro-1,3,5-triazin-2-ones, has been prepared and their structures have been determined for the first time. This family of compounds only differ in their substituent at the 5-position (which is derived from the corresponding primary amine), that is, methyl (1), ethyl (2), isopropyl (3), tert-butyl (4), benzyl (5), N,N-(diethyl)ethylamine (6), and 2-hydroxyethyl (7). The common heterocyclic core of these molecules is a cyclic urea, which has the potential to form a hydrogen-bonding tape motif that consists of self-associative R₂²(8) dimers. The results from X-ray crystallography and, where possible, Laue neutron crystallography show that the hydrogen-bonding motifs that are observed and the planarity of the hydrogen bonds appear to depend on the steric hindrance at the α-carbon atom of the N substituent. With the less-hindered substituents, methyl and ethyl, the anticipated tape motif is observed. When additional methyl groups are added onto the α-carbon atom, as in the isopropyl and tert-butyl derivatives, a different 2D hydrogen-bonding motif is observed. Despite the bulkiness of the substituents, the benzyl and N,N-(diethyl)ethylamine derivatives have methylene units at the α-carbon atom and, therefore, display the tape motif. The introduction of a competing hydrogen-bond donor/acceptor in the 2-hydroxyethyl derivative disrupts the tape motif, with a hydroxy group interrupting the N-H···O=C interactions. The geometry around the hydrogen-bearing nitrogen atoms, whether planar or non-planar, has been confirmed for compounds 2 and 5 by using Laue neutron diffraction and rationalized by using computational methods, thus demonstrating that distortion of O-C-N-H torsion angles occurs to maintain almost-linear hydrogen-bonding interactions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ANAEROBIC BIODEGRADATION OF MTBE AT A GASOLINE SPILL SITE

EPA Science Inventory

To manage risk or to implement natural attenuation as a remedy, regulatory agencies must understand the processes that attenuate methyl-tert-butyl ether (MTBE) in ground water. Most case studies and laboratory studies in the literature indicate that natural biodegradation is not ...

OBSERVATIONS FROM CONTAMINANT PLUMES ON LONG ISLAND

EPA Science Inventory

The aquifers of Long Island serve as a sole source drinking water supply for the entire
local population of about three million people. Where the shallow Upper Glacial Aquifer has been contaminated with petroleum hydrocarbons and methyl tert-butyl ether (MTBE), intensive site ...

COST OF MTBE REMEDIATION

EPA Science Inventory

Widespread contamination of methyl tert-butyl ether (MTBE) in ground water has raised concerns about the increased cost of remediation of MTBE releases compared to BTEX-only sites. To evaluate these cost, cost information for 311 sites was furnished by U.S. EPA Office of Undergr...

COSTS TO REMEDIATE MTBE-CONTAMINATED SITES

EPA Science Inventory

The extensive contamination of methyl tert-butyl ether (MTBE) in ground water has introduced concerns about the increased cost of remediation of MTBE releases compared to sites with BTEX only contamination. In an attempt to evaluate these costs, cost information for 311 sites wa...

Discovery, Synthesis, And Structure-Based Optimization of a Series of N-(tert-Butyl)-2-(N-arylamido)-2-(pyridin-3-yl) Acetamides (ML188) as Potent Noncovalent Small Molecule Inhibitors of the Severe Acute Respiratory Syndrome Coronavirus (SARS-CoV) 3CL Protease

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

Jacobs, Jon; Grum-Tokars, Valerie; Zhou, Ya

A high-throughput screen of the NIH molecular libraries sample collection and subsequent optimization of a lead dipeptide-like series of severe acute respiratory syndrome (SARS) main protease (3CLpro) inhibitors led to the identification of probe compound ML188 (16-(R), (R)-N-(4-(tert-butyl)phenyl)-N-(2-(tert-butylamino)-2-oxo-1-(pyridin-3-yl)ethyl)furan-2-carboxamide, Pubchem CID: 46897844). But, unlike the majority of reported coronavirus 3CLpro inhibitors that act via covalent modification of the enzyme, 16-(R) is a noncovalent SARS-CoV 3CLpro inhibitor with moderate MW and good enzyme and antiviral inhibitory activity. A multicomponent Ugi reaction was utilized to rapidly explore structure–activity relationships within S1', S1, and S2enzyme binding pockets. Moreover, the X-ray structure of SARS-CoV 3CLpromore » bound with 16-(R) was instrumental in guiding subsequent rounds of chemistry optimization. 16-(R) provides an excellent starting point for the further design and refinement of 3CLpro inhibitors that act by a noncovalent mechanism of action.« less

LASERS IN MEDICINE: Quantum efficiency of the laser-excited singlet-oxygen-sensitised delayed fluorescence of the zinc complex of tetra(4-tert-butyl)phthalocyanine

NASA Astrophysics Data System (ADS)

Bashtanov, M. E.; Drozdova, N. N.; Krasnovskii, A. A.

1999-12-01

An investigation was made of the ratios of the intensity Idf of the singlet-oxygen(1O2)-sensitised delayed fluorescence of the zinc complex of tetra(4-tert-butyl)phthalocyanine (ZnTBPc), with the maximum at λ = 685 nm, to the intensity I1270 of the photosensitised phosphorescence of 1O2 with the maximum at λ = 1270 nm in deuterated benzene when excited with λ = 337 nm nitrogen-laser pulses. Depending on the energy density of the laser radiation (0.25 — 0.7 mJ cm-2) and on the concentration of ZnTBPc (0.06 — 3.4 μM), the ratio of the zero-time intensities of the delayed fluorescence of ZnTBPc and of the singlet-oxygen phosphorescence Idf0/I12700 varied from 0.01 to 0.2 in air-saturated solutions of ZnTBPc. The intensity Idf0 decreased fivefold as a result of saturation with oxygen of air-saturated solutions. The quantum efficiency of the delayed fluorescence was represented by the coefficient α =(Idf0/I12700)kr/(γf[1O2]0[ZnTBPc]), where [1O2]0 is the zero-time concentration of 1O2 after a laser shot; kr is the rate constant of radiative deactivation of 1O2 in the investigated solvent; γf is the quantum yield of the ZnTBPc fluorescence. It was established that in the case of air-saturated solutions of ZnTBPc this coefficient was approximately 200 times less than for metal-free tetra(4-tert-butyl)phthalocyanine and its absolute value was ~2 × 1011 M-2 s-1.

Enzymatic production of monoacylglycerols containing polyunsaturated fatty acids through an efficient glycerolysis system.

PubMed

Yang, Tiankui; Rebsdorf, Morten; Engelrud, Ulrik; Xu, Xuebing

2005-03-09

The aim of the study was to develop an efficient glycerolysis system for the enzymatic production of monoacylglycerols (MAGs) containing polyunsaturated fatty acids. Glycerolysis has been widely applied in industry for the chemical production of food MAGs under high temperature. The enzymatic glycerolysis system at 40-70 degrees C is unfortunately a multiphase system, which leads to the lower reaction efficiency. A tert-butyl alcohol system was developed after careful evaluation and more than 20-fold of the reaction efficiency from this system was obtained compared to the solvent-free system. Novozym 435 was employed as a catalyst in the glycerolysis from the screening. In the batch reaction system with tert-butyl alcohol, temperature higher than 40 degrees C was favored. The glycerol/oil ratio was best in the study with 4.5 while the solvent weight ratio from 1 to 3 had little effect. In general, 60-70% yield can be obtained at 2 h in the stirred tank reactor. The continuous glycerolysis was conducted in a packed bed reactor. MAG yield up to 70% was reached at 30-40 min residence time. The continuous glycerolysis was more sensitive to the amount of tert-butyl alcohol, and in the weight ratio to oil more than 2 was favored. The continuous process was optimized with the assistance of response surface methodology. Optimal conditions for the packed bed reactor after all considerations were recommended as glycerol/oil 4:1 (mol/mol), temperature 40 degrees C, and residence time 45 min. The operation stability study showed that there was no slight reduction of reaction performance at more than 30 days, implying a high feasibility in practical applications.

Low-coordinate rare-earth complexes of the asymmetric 2,4-di-tert-butylphenolate ligand prepared by redox transmetallation/protolysis reactions, and their reactivity towards ring-opening polymerisation.

PubMed

Clark, Lawrence; Deacon, Glen B; Forsyth, Craig M; Junk, Peter C; Mountford, Philip; Townley, Josh P

2010-08-07

New trivalent lanthanoid aryloxide complexes have been prepared by redox transmetallation/protolysis (rtp) reactions using 2,4-di-tert-butylphenol (dbpH). Mononuclear octahedral complexes from tetrahydrofuran (thf) were of the type [Ln(dbp)(3)(thf)(3)] (Ln = La (1), Pr (2), Nd (3), Gd (4), Er (5)). The lanthanoid contraction results in the rather subtle change in stereochemistry from meridional (La, Pr, Nd, Gd) to facial (Er). An analogous reaction with neodymium in dimethoxyethane (dme), resulted in the isolation of the seven coordinate [Nd(dbp)(3)(dme)(2)] (6), and this is comparable with the thf complexes in terms of steric crowding. Dinuclear complexes of the type [Ln(2)(dbp)(6)(thf)(2)], (Ln = Nd (7), Er (8)) were obtained when 1 and 5 were recrystallised from toluene. These dimeric complexes contain two bridging and four terminal phenolates, as well as a single coordinated molecule of thf at each metal. A similar structural motif was observed for the products when the reaction was performed in diethyl ether, and in the absence of a solvent, yielding [Nd(2)(dbp)(6)(Et(2)O)(2)] (9) and [Nd(2)(dbp)(6)(dbpH)(2)] (10) respectively. Complexes 3 and 4 alone were efficient but poorly-controlled initiators for the ROP of rac-lactide, but with an excess of BnOH as a co-initiator they showed features consistent with immortal polymerisation. Use of BnNH(2) led to well-controlled, amine-initiated immortal ROP of rac-lactide, only the second report of this type of process for a group 3 or lanthanoid system.

Defining the electronic and geometric structure of one-electron oxidized copper-bis-phenoxide complexes.

PubMed

Storr, Tim; Verma, Pratik; Pratt, Russell C; Wasinger, Erik C; Shimazaki, Yuichi; Stack, T Daniel P

2008-11-19

The geometric and electronic structure of an oxidized Cu complex ([CuSal](+); Sal = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV-vis-NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal](+) (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal](+), affording exclusively a Cu(III) species in the solid state (4-300 K). Variable-temperature solution studies suggest that [CuSal](+) exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal(*)](+) (S = 1) and the high-valent metal form [Cu(III)Sal](+) (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine-bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSal(red)](+) (Sal(red) = N,N'-bis(3,5-di- tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)-ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu-bis-phenoxide complexes.

Defining the Electronic and Geometric Structure of One-Electron Oxidized Copper–Bis-phenoxide Complexes

PubMed Central

Storr, Tim; Verma, Pratik; Pratt, Russell C.; Wasinger, Erik C.; Shimazaki, Yuichi; Stack, T. Daniel P.

2009-01-01

The geometric and electronic structure of an oxidized Cu complex ([CuSal]+; Sal = N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV–vis–NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal]+ (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal]+, affording exclusively a Cu(III) species in the solid state (4–300 K). Variable-temperature solution studies suggest that [CuSal]+ exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal•]+ (S = 1) and the high-valent metal form [Cu(III)Sal]+ (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine–bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSalred]+ (Salred = N, N′-bis(3,5-di-tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)–ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu–bis-phenoxide complexes. PMID:18939830

Low Temperature, Selective Atomic Layer Deposition of Nickel Metal Thin Films.

PubMed

Kerrigan, Marissa M; Klesko, Joseph P; Blakeney, Kyle J; Winter, Charles H

2018-04-25

We report the growth of nickel metal films by atomic layer deposition (ALD) employing bis(1,4-di- tert-butyl-1,3-diazadienyl)nickel and tert-butylamine as the precursors. A range of metal and insulating substrates were explored. An initial deposition study was carried out on platinum substrates. Deposition temperatures ranged from 160 to 220 °C. Saturation plots demonstrated self-limited growth for both precursors, with a growth rate of 0.60 Å/cycle. A plot of growth rate versus substrate temperature showed an ALD window from 180 to 195 °C. Crystalline nickel metal was observed by X-ray diffraction for a 60 nm thick film deposited at 180 °C. Films with thicknesses of 18 and 60 nm grown at 180 °C showed low root mean square roughnesses (<2.5% of thicknesses) by atomic force microscopy. X-ray photoelectron spectroscopies of 18 and 60 nm thick films deposited on platinum at 180 °C revealed ionizations consistent with nickel metal after sputtering with argon ions. The nickel content in the films was >97%, with low levels of carbon, nitrogen, and oxygen. Films deposited on ruthenium substrates displayed lower growth rates than those observed on platinum substrates. On copper substrates, discontinuous island growth was observed at ≤1000 cycles. Film growth was not observed on insulating substrates under any conditions. The new nickel metal ALD procedure gives inherently selective deposition on ruthenium and platinum from 160 to 220 °C.

40 CFR 60.667 - Chemicals affected by subpart NNN.

Code of Federal Regulations, 2012 CFR

2012-07-01

... fractions n-Butane 106-97-8 1,4-Butanediol 110-63-4 Butanes, mixed 1-Butene 106-98-9 2-Butene 25167-67-3 Butenes, mixed n-Butyl acetate 123-86-4 Butyl acrylate 141-32-2 n-Butyl alcohol 71-36-3 sec-Butyl alcohol... Diethanolamine 111-42-2 Diethylbenzene 25340-17-4 Diethylene glycol 111-46-6 Di-n-heptyl-n-nonyl undecyl...

Isolation of tert-alkylphenols from the products of alkylation of phenols

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

Nesterova, T.N.; Verevkin, S.P.; Rempel', R.D.

1987-08-10

The authors studied the conditions of isolation of tert-amyl-, hexyl-, heptyl-, octyl-, decyl-, and dodecylphenols, and tert-alkylcresols, alkylpyrocatechols, and alkylhydroquinones from alkylation products. The compounds were isolated in all cases from reaction mixtures obtained in presence of cation-exchange resins of the KU-2 type. A preliminary stage, flash evaporation of the reaction mass at 4-13 Pa for 5-15 min, is needed to prevent decomposition of tert-alkylphenols during their isolation from acid reaction mixtures by fractionation. Flash distillation of high-boiling tert-alkylphenols should be conducted in presence of a component lowering the boiling point of the mixture, added in 1:(0.5-1.0) weight ratio ofmore » original mixture to the component.« less

Synthesis and fluorescence emission properties of 1,3,6,8-tetraarylpyrenes

NASA Astrophysics Data System (ADS)

Hu, Jian-Yong; Feng, Xing; Tomiyasu, Hirotsugu; Seto, Nobuyuki; Rayhan, Ummey; Elsegood, Mark R. J.; Redshaw, Carl; Yamato, Takehiko

2013-09-01

Three types of stable pyrene-based highly fluorescence (blue) compounds, 1-, 1,6-bis, 1,8-bis and 1,3,6,8-tetrakis(7-tert-butylpyrenyl)pyrenes and 1,3,6,8-tetrakis[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]pyrene, were successfully synthesized via a Pd/Cu-catalysed Suzuki cross-coupling reaction of the corresponding bromopyrenes with 7-tert-butyl-1-pyrenylboronic ester or 2-[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]-4,4,5,5-tetramethyl[1,3,2]dioxaborolane, respectively. All compounds have good solubility in common organic solvents and high thermal stability with melting points up to 270 °C; the exceptions are the isomeric 1,6-bis-, and 1,8-bispyrenyl-substituted pyrenes. All products show high extinction coefficients of absorption (λmax ≈ 349-396 nm) and high quantum yields (λmax ≈ 432-465 nm; Φf ≈ 0.75-0.99) in dichloromethane solution, and emit strong fluorescence in the visible region ranging from deep-blue to pure-blue on increasing the number of substituents. This data suggests that such systems have promise as blue emitters in organic light-emitting device (OLED) applications (OLED = organic light emitting diode). Crystal structures were determined for 1,3,6,8-tetrakis [9,9-bis(3-methylbutyl)-9H-fluoren-2-yl] pyrene and 1,3,6,8-tetrakis(4-methoxyphenyl)pyrene.

Sensitive multiresidue method by HS-SPME/GC-MS for 10 volatile organic compounds in urine matrix: a new tool for biomonitoring studies on children.

PubMed

Antonucci, Arianna; Vitali, Matteo; Avino, Pasquale; Manigrasso, Maurizio; Protano, Carmela

2016-08-01

A HS-SPME method coupled with GC-MS analysis has been developed for simultaneously measuring the concentration of 10 volatile organic compounds (VOCs) (benzene, toluene, ethylbenzene, o-, m-, and p-xylene, methyl tert-butyl ether, ethyl tert-butyl ether, 2-methyl-2-butyl methyl ether, and diisopropyl ether) in urine matrix as a biomonitoring tool for populations at low levels of exposure to such VOCs. These compounds, potentially toxic for human health, are common contaminants of both outdoor and indoor air, as they are released by autovehicular traffic; some of them are also present in environmental tobacco smoke (ETS). Thus, the exposure to these pollutants cannot be neglected and should be assessed. The low limits of detection and quantification (LODs and LOQs <6.5 and 7.5 ng L(-1), respectively) and the high reproducibility (CVs <4 %) make the developed method suited for biomonitoring populations exposed at low levels such as children. Further, the method is cost-effective and low in time-consumption; therefore, it is useful for investigating large populations. It has been applied to children exposed to traffic pollution and/or ETS; the relevant results are reported, and the relevant implications are discussed.

TRANSPORT OF METHYL TERT-BUTYL ETHER THROUGH ALFALFA PLANTS. (R825549C062)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

HYDROLYSIS OF MTBE TO TBA IN GROUND WATER SAMPLES WITH HYDROCHLORIC ACID

EPA Science Inventory

Conventional sampling and analytical protocols have poor sensitivity for fuel oxygenates that are alcohols, such as tert-butyl alcohol (TBA). Because alcohols are miscible or highly soluble in water, alcohols are not efficiently transferred to the gas chromatograph for analysis....

SUMMARY OF WORKSHOP ON BIODEGRADATION OF MTBE FEBRUARY 1-3, 2000

EPA Science Inventory

A workshop on biodegradation of methyl tert butyl ether (MTBE) contaminated soils and groundwater was held in Cincinnati, Ohio, February 1-2, 2000, and was sponsored by the USEPA's NRMRL and the American Petroleum Institute. Researchers in academia, industry, and government were ...

Analysis of Fluorotelomer Alcohols in Soils: Optimization of Extraction and Chromatography

EPA Science Inventory

This article describes the development of an analytical method for the determination of fluorotelomer alcohols (FTOHs) in soil. The sensitive and selective determination of the telomer alcohols was performed by extraction with mthyl tert-butyl ether (MTBE) and analysis of the ext...

Provisional Peer-Reviewed Toxicity Values for Tert Butyl Formate

EPA Science Inventory

Provisional Peer-Reviewed Toxicity Values (PPRTV) assessments are developed for use by the Agency’s Office of Land and Emergency Management (OLEM) to support informed decisions in the Superfund program and at hazardous waste sites when a values is not available in the Integrated ...

Optimization of headspace solid-phase microextraction by means of an experimental design for the determination of methyl tert.-butyl ether in water by gas chromatography-flame ionization detection.

PubMed

Dron, Julien; Garcia, Rosa; Millán, Esmeralda

2002-07-19

A procedure for determination of methyl tert.-butyl ether (MTBE) in water by headspace solid-phase microextraction (HS-SPME) has been developed. The analysis was carried out by gas chromatography with flame ionization detection. The extraction procedure, using a 65-microm poly(dimethylsiloxane)-divinylbenzene SPME fiber, was optimized following experimental design. A fractional factorial design for screening and a central composite design for optimizing the significant variables were applied. Extraction temperature and sodium chloride concentration were significant variables, and 20 degrees C and 300 g/l were, respectively chosen for the best extraction response. With these conditions, an extraction time of 5 min was sufficient to extract MTBE. The calibration linear range for MTBE was 5-500 microg/l and the detection limit 0.45 microg/l. The relative standard deviation, for seven replicates of 250 microg/l MTBE in water, was 6.3%.

Arbuscular mycorrhizal fungi in a wetland constructed for benzene-, methyl tert-butyl ether- and ammonia-contaminated groundwater bioremediation

PubMed Central

Fester, Thomas

2013-01-01

Arbuscular mycorrhizal fungi (AMF), which are present in most natural environments, have demonstrated capacity to promote biodegradation of organic pollutants in the greenhouse. However, it is not certain whether AMF can spontaneously establish in phytoremediation systems constructed to decontaminate groundwater, because of the unusual conditions during the construction and operation of such systems. To assess this possibility, root samples from a wetland constructed for the phytoremediation of groundwater contaminated with benzene, methyl tert-butyl ether and ammonia were analysed. Substantial AMF colonization was observed in plant roots sampled close to the inlet of a basin filled with fine gravel and planted with Phragmites australis. In addition, analysis of a fragment of the nuclear large ribosomal subunit, amplified by nested PCR, revealed the presence of AMF molecular operational taxonomic units closely related to Funneliformis mosseae and Rhizophagus irregularis in the samples. These findings demonstrate the capacity of generalist AMF strains to establish spontaneously, rapidly and extensively in groundwater bioremediation technical installations. PMID:22846140

Microbial biosafety of pilot-scale bioreactor treating MTBE and TBA-contaminated drinking water supply.

PubMed

Schmidt, Radomir; Klemme, David A; Scow, Kate; Hristova, Krassimira

2012-03-30

A pilot-scale sand-based fluidized bed bioreactor (FBBR) was utilized to treat both methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) from a contaminated aquifer. To evaluate the potential for re-use of the treated water, we tested for a panel of water quality indicator microorganisms and potential waterborne pathogens including total coliforms, Escherichia coli, Salmonella and Shigella spp., Campylobacter jejuni, Aeromonas hydrophila, Legionella pneumophila, Vibrio cholerae, Yersinia enterocolytica and Mycobacterium avium in both influent and treated waters from the bioreactor. Total bacteria decreased during FBBR treatment. E. coli, Salmonella and Shigella spp., C. jejuni, V. cholerae, Y. enterocolytica and M. avium were not detected in aquifer water or bioreactor treated water samples. For those pathogens detected, including total coliforms, L. pneumophila and A. hydrophila, numbers were usually lower in treated water than influent samples, suggesting removal during treatment. The detection of particular bacterial species reflected their presence or absence in the influent waters. Copyright © 2012 Elsevier B.V. All rights reserved.

Polymer brush covalently attached to OH-functionalized mica surface via surface-initiated ATRP: control of grafting density and polymer chain length.

PubMed

Lego, Béatrice; François, Marion; Skene, W G; Giasson, Suzanne

2009-05-05

The controlled grafting density of poly(tert-butyl acrylate) was studied on OH-activated mica substrates via surface-initiated atom-transfer radical polymerization (ATRP). By properly adjusting parameters such as the immobilization reaction time and the concentration of an ATRP initiator, a wide range of initiator surface coverages and hence polymer densities on mica were possible. The covalently immobilized initiator successfully promoted the polymerization of tert-butyl acrylate on mica surfaces. The resulting polymer layer thickness was measured by AFM using a step-height method. Linear relationships of the polymer thickness with respect to the molecular weight of the free polymer and with respect to the monomer conversion were observed, suggesting that ATRP is well controlled and relatively densely end-grafted layers were obtained. The polymer grafting density controlled by adjusting the initiator surface coverage was confirmed by the polymer layer swelling capacity and film thickness measurements.

Protective Effects of Black Rice Extracts on Oxidative Stress Induced by tert-Butyl Hydroperoxide in HepG2 Cells

PubMed Central

Lee, Seon-Mi; Choi, Youngmin; Sung, Jeehye; Kim, Younghwa; Jeong, Heon-Sang; Lee, Junsoo

2014-01-01

Black rice contains many biologically active compounds. The aim of this study was to investigate the protective effects of black rice extracts (whole grain extract, WGE and rice bran extract, RBE) on tert-butyl hydroperoxide (TBHP)-induced oxidative injury in HepG2 cells. Cellular reactive oxygen species (ROS), antioxidant enzyme activities, malondialdehyde (MDA) and glutathione (GSH) concentrations were evaluated as biomarkers of cellular oxidative status. Cells pretreated with 50 and 100 μg/mL of WGE or RBE were more resistant to oxidative stress in a dose-dependent manner. The highest WGE and BRE concentrations enhanced GSH concentrations and modulated antioxidant enzyme activities (glutathione reductase, glutathione-S-transferase, catalase, and superoxide dismutase) compared to TBHP-treated cells. Cells treated with RBE showed higher protective effect compared to cells treated with WGE against oxidative insult. Black rice extracts attenuated oxidative insult by inhibiting cellular ROS and MDA increase and by modulating antioxidant enzyme activities in HepG2 cells. PMID:25580401

Methyl tert-butyl ether (MTBE) in finished drinking water in Germany.

PubMed

Kolb, Axel; Püttmann, Wilhelm

2006-03-01

In the present study 83 finished drinking water samples from 50 cities in Germany were analyzed for methyl tert-butyl ether (MTBE) content with a detection limit of 10 ng/L. The detection frequency was 46% and the concentrations ranged between 17 and 712 ng/L. Highest concentrations were found in the community water systems (CWSs) of Leuna and Spergau in Saxony-Anhalt. These CWSs are supplied with water possibly affected by MTBE contaminated groundwater. MTBE was detected at concentrations lower than 100 ng/L in drinking water supplied by CWSs using bank filtered water from Rhine and Main Rivers. The results from Leuna and Spergau show that large groundwater contaminations in the vicinity of CWSs pose the highest risk for MTBE contamination in drinking water. CWSs using bank filtered water from Rhine and Main Rivers are susceptible to low MTBE contaminations in finished drinking water. All measured MTBE concentrations were below proposed limit values for drinking water.

Water- and air-quality and surficial bed-sediment monitoring of the Sweetwater Reservoir watershed, San Diego County, California, 2003-09

USGS Publications Warehouse

Mendez, Gregory O.; Majewski, Michael S.; Foreman, William T.; Morita, Andrew Y.

2015-01-01

Sampling results show concentrations of the gasoline oxygenate methyl tert-butyl ether in water and air samples declined after it was phased out by the State of California in January 2004. The largest concentrations of gasoline hydrocarbons benzene and toluene in water were detected at or near the surface of the SWR. Isophorone and phenol were the two most frequently detected BNA compounds in water. Diuron, prometon, and simazine were the most frequently detected pesticide compounds in water. Concentrations of benzene and toluene in air samples were highest during the cooler months and had a consistent seasonal pattern over time. Ten PAH compounds were detected frequently in air samples. Twelve pesticide compounds were also detected in air samples. Surficial bed-sediment samples were analyzed for 53 PAHs; 22 of the compounds had one or more detections. Surficial bed-sediment samples were analyzed for 22 organic compounds; only 6 compounds had one or more detections. Surficial bed-sediment samples were analyzed for 37 metals.

Development and application of a rat PBPK model to elucidate kidney and liver effects induced by ETBE and tert-butanol.

PubMed

Salazar, Keith D; Brinkerhoff, Christopher J; Lee, Janice S; Chiu, Weihsueh A

2015-11-01

Subchronic and chronic studies in rats of the gasoline oxygenates ethyl tert-butyl ether (ETBE) and tert-butanol (TBA) report similar noncancer kidney and liver effects but differing results with respect to kidney and liver tumors. Because TBA is a major metabolite of ETBE, it is possible that TBA is the active toxic moiety in all these studies, with reported differences due simply to differences in the internal dose. To test this hypothesis, a physiologically-based pharmacokinetic (PBPK) model was developed for ETBE and TBA to calculate internal dosimetrics of TBA following either TBA or ETBE exposure. This model, based on earlier PBPK models of methyl tert-butyl ether (MTBE), was used to evaluate whether kidney and liver effects are consistent across routes of exposure, as well as between ETBE and TBA studies, on the basis of estimated internal dose. The results demonstrate that noncancer kidney effects, including kidney weight changes, urothelial hyperplasia, and chronic progressive nephropathy (CPN), yielded consistent dose-response relationships across routes of exposure and across ETBE and TBA studies using TBA blood concentration as the dose metric. Relative liver weights were also consistent across studies on the basis of TBA metabolism, which is proportional to TBA liver concentrations. However, kidney and liver tumors were not consistent using any dose metric. These results support the hypothesis that TBA mediates the noncancer kidney and liver effects following ETBE administration; however, additional factors besides internal dose are necessary to explain the induction of liver and kidney tumors. Published by Elsevier Inc.

ENZYMATIC POLYMERIZATION OF PHENOLS IN ROOM TEMPERATURE IONIC LIQUIDS

PubMed Central

Eker, Bilge; Zagorevski, Dmitri; Zhu, Guangyu; Linhardt, Robert J.; Dordick, Jonathan S.

2009-01-01

Soybean peroxidase (SBP) was used to catalyze the polymerization of phenols in room-temperature ionic liquids (RTILs). Phenolic polymers with number average molecular weights ranging from 1200 to 4100 D were obtained depending on the composition of the reaction medium and the nature of the phenol. Specifically, SBP was highly active in methylimidazolium-containing RTILs, including 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(BF4)), and 1-butyl-3-methylpyridinium tetrafluoroborate (BMPy(BF4)) with the ionic liquid content as high as 90% (v/v); the balance being aqueous buffer. Gel permeation chromatography and MALDI-TOF analysis indicated that higher molecular weight polymers can be synthesized in the presence of higher RTIL concentrations, with selective control over polymer size achieved by varying the RTIL concentration. The resulting polyphenols exhibited high thermostability and possessed thermosetting properties. PMID:20161409

40 CFR 721.7220 - Polymer of substituted phenol, formaldehyde, epichlorohydrin, and disubstituted benzene.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymer of substituted phenol... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.7220 Polymer of substituted phenol... subject to reporting. (1) The chemical substance identified generically as polymer of substituted phenol...

PRESENTED AT THE TRIANGLE CONSORTIUM FOR REPRODUCTIVE BIOLOGY MEETING ON 2/11/06: DI(N-BUTYL) PHTHALATE AND DIETHYLHEXYL PHTHALATE IN COMBINATION ALTER SEXUAL DIFFERENTIATION IN A CUMULATIVE MANNER AS A RESULT OF DEPRESSED FETAL TESTOSTERONE PRODUCTION AND INSL3 GENE EXPRESSION IN MALE RATS

EPA Science Inventory

Plasticizers di(n-butyl) phthalate (DBP) and diehtylhexyl phthalate (DEHP) have similar modes of action: in utero exposure reduces testosterone (T) production in fetal male rats, inhibits reproductive tract differentiation, and induces reproductive organ malformations. In utero e...

Di-iso-Butyl Phthalate MATERNAL AND FETAL DATA FROM ...

EPA Pesticide Factsheets

this file contains the raw data on the effects of in utero administration of di-iso-butyl phthalate on maternal weight gain during dosing and the numbers of fetuses and fetal resorptions. The data have all been previously published, as described on the file metadata sheet. Raw data file from our published studies on DIBP specifically requested (6/14/2016) by NCEA scientists for analysis and inclusion in their assessment of this chemical.

Kinetic studies of the impact of thiocyanate moiety on the catalytic properties of Cu(II) and Fe(III) complexes of a new Mannich base

NASA Astrophysics Data System (ADS)

Ayeni, Ayowole O.; Watkins, Gareth M.

2018-04-01

Four new metal complexes of a novel Mannich base 5-methyl-2-((4-(pyridin-2-yl)piperazin-1-yl)methyl)phenol (HL) have been prepared. The compounds were characterized by an array of analytical and spectroscopic methods including Nuclear Magnetic Resonance, Infra-red and UV-Visible spectroscopy. Compounds 1-4 behaved as effective catalysts towards the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to its corresponding quinone in the presence of molecular oxygen in DMF solution while compound 4 proved to be the best catalyst with a turnover rate of 17.93 ± 1.10 h-1 as other complexes showed lower rates of oxidation. Also with the exception of dinuclear iron complex (4); thiocyanate containing Cu(II) complex exhibited lower catecholase activity compared to the Cu(II) complex without it.

Abiotic Reductive Dechlorination of Tetrachloroethylene and Trichloroethylene in Anaerobic Environments

DTIC Science & Technology

2009-01-15

Measurement of Henry’s Law Constant for methyl tert-butyl ether Using Solid-phase Microextraction. Environmental Toxicology and Chemistry 2001, 20, 1625...and Environmental Microbiology 2005, 71, 3413-3419. Nirmalakhandan, N. N., R. E. Speece. QSAR Model for Predicting Henry’s Constant. Environmental

Quantifying residues from postharvest fumigation of almonds and walnuts with propylene oxide

USDA-ARS?s Scientific Manuscript database

A novel analytical approach, involving solvent extraction with methyl tert-butyl ether (MTBE) followed by gas chromatography (GC), was developed to quantify residues that result from the postharvest fumigation of almonds and walnuts with propylene oxide (PPO). Verification and quantification of PPO,...

DECISION-MAKING, SCIENCE AND GASOLINE ADDITIVES

EPA Science Inventory

Methyl-tert butyl ether (MTBE) has been used as a gasoline additive to serve two major purposes. The first use was as an octane-enhancer to replace organic lead, beginning in 1979. The second use, which began about 1992, was as an oxygenated additive to meet requirements ...

USE OF MEMBRANE BIOREACTOR FOR BIODEGRADATION OF MTBE IN CONTAMINATED WATER1

EPA Science Inventory

An ultrafiltration membrane bioreactor was evaluated for biodegradation of methyl tert-butyl ether (MTBE) in contaminated water. The system was fed 5 mg/L MTBE in granular activated carbon (GAC) treated Cincinnati tap water containing ample buffer and nutrients. Within 120...

IRIS Toxicological Review and Summary Documents for Methyl Tert-Butyl Ether (MTBE)

EPA Science Inventory

MTBE is a volatile organic chemical used to oxygenate gasoline. Oxygenated gasoline improves the exhaust emissions from gasoline engines. Since 1992 it has been used to comply with the Federal Reformulated Gasoline (begun in 1995) and Wintertime Oxygenated Fuel (begun in 1992) p...

REMEDIAL COSTS FOR MTBE IN SOIL AND GROUND WATER

EPA Science Inventory

Widespread contamination of methyl tert-butyl ether (MTBE) in ground water has raised concerns about the increased cost of remediation of MTBE releases compared to BTEX-only sites. To evaluate these costs, cost information for 311 sites was furnished by U.S. EPA Office of Underg...

Mechanistic aspects of hydrogen abstraction for phenolic antioxidants. Electronic structure and topological electron density analysis.

PubMed

Singh, Nakul; O'Malley, Patrick J; Popelier, Paul L A

2005-02-21

Density functional calculations using the B3LYP functional are used to provide insight into the hydrogen abstraction mechanism of phenolic antioxidants. The energy profiles for 13 ortho, meta, para and di-methyl substituted phenols with hydroperoxyl radical have been determined. An excellent correlation between the enthalpy (DeltaH) and activation energy (DeltaEa) was found, obeying the Evans-Polanyi rule. The effects of hydrogen bonding on DeltaEa are also discussed. Electron donating groups at the ortho and para positions are able to lower the activation energy for hydrogen abstraction. The highly electron withdrawing fluoro substituent increases the activation energies relative to phenol at the meta position but not at the para position. The electron density is studied using the atoms in molecules (AIM) approach. Atomic and bond properties are extracted to describe the hydrogen atom abstraction mechanism. It is found that on going from reactants to transition state, the hydrogen atom experiences a loss in volume, electronic population and dipole moment. These features suggest that the phenol hydroperoxyl reactions proceed according to a proton coupled electron transfer (PCET) as opposed to a hydrogen atom transfer (HAT) mechanism.

Phytochemicals: Extraction, Isolation, and Identification of Bioactive Compounds from Plant Extracts

PubMed Central

Altemimi, Ammar; Lakhssassi, Naoufal; Baharlouei, Azam; Watson, Dennis G.; Lightfoot, David A.

2017-01-01

There are concerns about using synthetic phenolic antioxidants such as butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) as food additives because of the reported negative effects on human health. Thus, a replacement of these synthetics by antioxidant extractions from various foods has been proposed. More than 8000 different phenolic compounds have been characterized; fruits and vegetables are the prime sources of natural antioxidants. In order to extract, measure, and identify bioactive compounds from a wide variety of fruits and vegetables, researchers use multiple techniques and methods. This review includes a brief description of a wide range of different assays. The antioxidant, antimicrobial, and anticancer properties of phenolic natural products from fruits and vegetables are also discussed. PMID:28937585

Total phenolics and antioxidant activities of fenugreek, green tea, black tea, grape seed, ginger, rosemary, gotu kola, and ginkgo extracts, vitamin E, and tert-butylhydroquinone.

PubMed

Rababah, Taha M; Hettiarachchy, Navam S; Horax, Ronny

2004-08-11

The total phenolics and antioxidant activities of fenugreek, green tea, black tea, grape seed, ginger, rosemary, gotu kola, and ginkgo extracts, vitamin E, and tert-butylhydroquinone, were determined. Grape seed and green tea were analyzed for their phenolic constituents using high-performance liquid chromatography. The total phenolics of the plant extracts, determined by the Folin-Ciocalteu method, ranged from 24.8 to 92.5 mg of chlorogenic acid equivalent/g dry material. The antioxidant activities of methanolic extracts determined by conjugated diene measurement of methyl linoleate were 3.4-86.3%. The antioxidant activity of the extracts using chicken fat by an oxidative stability instrument (4.6-10.2 h of induction time) followed a similar trend in antioxidant activity as determined by the Folin-Ciocalteu method. Seven phenolics in grape seed and green tea extracts were identified that ranged from 15.38 to 1158.49 and 18.3 to 1087.02 mg/100 g of extract, respectively. Plant extracts such as green tea and grape seed extracts can be used to retard lipid oxidation in a variety of food products.

Exploring the potential of fulvalene dimetals as platforms for molecular solar thermal energy storage: computations, syntheses, structures, kinetics, and catalysis.

PubMed

Börjesson, Karl; Ćoso, Dušan; Gray, Victor; Grossman, Jeffrey C; Guan, Jingqi; Harris, Charles B; Hertkorn, Norbert; Hou, Zongrui; Kanai, Yosuke; Lee, Donghwa; Lomont, Justin P; Majumdar, Arun; Meier, Steven K; Moth-Poulsen, Kasper; Myrabo, Randy L; Nguyen, Son C; Segalman, Rachel A; Srinivasan, Varadharajan; Tolman, Willam B; Vinokurov, Nikolai; Vollhardt, K Peter C; Weidman, Timothy W

2014-11-17

A study of the scope and limitations of varying the ligand framework around the dinuclear core of FvRu2 in its function as a molecular solar thermal energy storage framework is presented. It includes DFT calculations probing the effect of substituents, other metals, and CO exchange for other ligands on ΔHstorage . Experimentally, the system is shown to be robust in as much as it tolerates a number of variations, except for the identity of the metal and certain substitution patterns. Failures include 1,1',3,3'-tetra-tert-butyl (4), 1,2,2',3'-tetraphenyl (9), diiron (28), diosmium (24), mixed iron-ruthenium (27), dimolybdenum (29), and ditungsten (30) derivatives. An extensive screen of potential catalysts for the thermal reversal identified AgNO3 -SiO2 as a good candidate, although catalyst decomposition remains a challenge. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

LOCALIZED RECHARGE INFLUENCES ON MTBE TRANSPORT AND WELL PLACEMENT CONSIDERATIONS

EPA Science Inventory

Vertical characterization of a gasoline release site at East Patchogue, New York showed that methyl tert-butyl ether (MTBE) and aromatic plumes "dived" as they passed beneath a sand pit. That this behavior was caused by aquifer recharge was shown by two pieces of evidence. Fir...

MTBE OXIDATION BYPRODUCTS FROM THE TREATMENT OF SURFACE WATERS BY OZONATION AND UV-OZONATION

EPA Science Inventory

In recent years, there has been considerable concern over the release of methyl tert-butyl ether (MTBE), as gasoline additive, into the aquifers used as potable water sources. MTBE readily dissolves in water and has entered the environment via gasoline spills and leaking...

Particle Size Effects on Fenton Regeneration of MTBE-spent Activated Carbon

EPA Science Inventory

Fenton-driven regeneration of spent granular activated carbon (GAC) is a developing technology that may reduce water treatment costs. In this study, the effect of GAC particle size on Fenton-driven oxidation of methyl tert-butyl ether (MTBE)-spent GAC was evaluated. The GAC was...

AN EXPERIMENTAL STUDY OF PHYTOREMEDIATION OF METHYL-TERT-BUTYL-ETHER (MTBE) IN GROUNDWATER. (R825549C062)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

NOVEL EMBEDDED CERAMIC ELECTRODE SYSTEM TO ACTIVATE NANOSTRUCTURED TITANIUM DIOXIDE FOR DEGRADATION OF MTBE

EPA Science Inventory

A novel reactor combining a flame-deposited nanostructured titanium dioxide film and a set of embedded ceramic electrodes was designed, developed and tested for degradation of methyl tert-butyl ether (MTBE) in water. On applying a voltage to the ceramic electrodes, a surface coro...

RAPID MEASUREMENT OF AQUEOUS HYDROXYL RADICAL CONCENTRATIONS IN STEADY-STATE HO· FLUX SYSTEMS

EPA Science Inventory

The spin-trap compound a-(4-pyridyl-1-oxide)-N-tert-butyl-nitrone (4-POBN) is utilized for the detection and quantitation of the hydroxyl radical (HO·) in aqueous solution. Capillary electrophoresis enables rapid analysis of the probe compound. The thermally unstable HO· radical ...

Persulfate Oxidation of MTBE- and Chloroform-Spent Granular Activated Carbon

EPA Science Inventory

Activated persulfate (Na2S2O8) regeneration of methyl tert-butyl ether (MTBE) and chloroform-spent GAC was evaluated in this study. Thermal-activation of persulfate was effective and resulted in greater MTBE removal than either alkaline-activation or H2O2–persulfate binary mixtur...

Iron Amendment and Fenton Oxidation of MTBE-Spent Granular Activated Carbon

EPA Science Inventory

Fenton-driven regeneration of Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) involves Fe amendment to the GAC to catalyze H2O2 reactions and to enhance the rate of MTBE oxidation and GAC regeneration. Four forms of iron (ferric sulfate, ferric chloride, fer...

EXPERIMENTAL MEASUREMENT OF THE RATE OF METHYL TERT-BUTYL ETHER HYDROLYSIS IN SUB- AND SUPERCRITICAL WATER. (R826738)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

CHEMICAL DESTRUCTION OF MTBE USING FENTON'S REAGENT: EFFECT OF FERROUS IRON/HYDROGEN PEROXIDE RATIO

EPA Science Inventory

In previous laboratory experiments Fenton's Reagent (FR) was successfully used as the source of hydroxyl radicals (OH*) for chemical treatment of low concentrations of methyl tert-butyl ether (MTBE) in water. Although under certain conditions MTBE degradation levels as high as 99...

Composition and Behavior of Fuel Ethanol

EPA Science Inventory

Ethanol usage in the United States has increased due in part to the elimination of methyl tert-butyl ether from the fuel supply and to the mandates of Congress. Two samples, one each from a wet mill and a dry mill ethanol plant, were obtained before denaturing. Each of these ...

BTEX MTBE BIOREMEDIATION: BIONETS CONTAINING ISOLITE, PM1, SOLID OXYGEN SOURCE

EPA Science Inventory

Methyl tert-Butyl Ether (MTBE), a gasoline additive, is a persistent and foul tasting contaminate that is more mobile in ground water than BTEX . It, along with BTEX, is turning up at many American crossroads. This study's objective was to determine if biologically active in sit...

MTBE BIOREMEDIATION WITH BIONETS CONTAINING ISOLITE, PMI, SOS ON AIR

EPA Science Inventory

Methyl tert-Butyl Ether (MTBE), a gasoline additive, is a persistent and foul tasting contaminant that is more mobile in ground water than BTEX. It is turning up at many American crossroads. This study's objective was to determine if biologically active in situ Bionets could bior...

MTBE BIODEGRADATION IN A GRAVITY FLOW, HIGH-BIOMASS RETAINING BIOREACTOR

EPA Science Inventory

The aerobic biodegradation of methyl tert-butyl ether (MtBE), a widely used fuel oxygenate, was investigated using a pilot-scale biomass-retaining bioreactor called a Biomass Concentrator Reactor (BCR). The reactor was operated for a year at a flow rate of 2500 L/d on Ci...

CONTROLLED, SHORT-TERM DERMAL AND INHALATION EXPOSURE TO MTBE AND DIBROMOCHLOROMETHANE

EPA Science Inventory

The oxygenate methyl tert-butyl ether (MTBE) has been added to gasoline to meet national ambient air quality standards in those parts of the US that are non-compliant for carbon monoxide. Although MTBE has provided important health benefits in terms of reduced hazardous air po...

Bioconcentration potential of organic environmental chemicals in humans

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

Geyer, H.; Scheunert, I.; Korte, F.

1986-12-01

A list of environmental chemicals detectable in adipose tissue and/or milk of non-occupationally exposed humans is presented. Besides their physiochemical properties (n-octanol/water partition coefficient and water solubility), their acceptable daily intake (ADI) values, production figures, fate in the environment, concentrations in human adipose tissue, and data from total diet studies from market basket investigations are given. Average bioconcentration factors (BCF) of polychlorinated biphenyls (PCBs), 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), DDT, hexachlorobenzene (HCB), dieldrin, hexachlorocyclohexane isomers (alpha-HCH, beta-HCH, gamma-HCH, delta-HCH), pentachlorophenol (PCP), and 3,5-di-tert-butyl-4-hydroxytoluene (BHT) in human adipose tissue are calculated. The bioconcentration factors (wet wt basis) of these compounds are between 3 andmore » 47 times higher in humans than in rats. The environmental chemicals are divided into three groups in respect to their bioconcentration factors in human adipose tissue: group I, high BCF (greater than 100); group II, medium BCF (10-100); and group III, low BCF (less than 10). The bioconcentration factors are useful for hazard assessment of chemicals to humans.« less

Deprotonation of a Seemingly Hydridic Diborane(6) To Build a B-B Bond.

PubMed

Kaese, Thomas; Budy, Hendrik; Bolte, Michael; Lerner, Hans-Wolfram; Wagner, Matthias

2017-06-19

Deprotonation of the doubly arylene-bridged diborane(6) derivative 1H 2 with (Me 3 Si) 3 CLi or (Me 3 Si) 2 NK gives the B-B σ-bonded species M[1H] in essentially quantitative yields (THF, room temperature; M=Li, K, arylene=4,4'-di-tert-butyl-2,2'-biphenylylene). With nBuLi as the base, the yield of Li[1H] drops to 20 % and the 1,1-bis(9-borafluorenyl)butane Li[2H] is formed as a side product (30 %). In addition to the 1,1-butanediyl fragment, the two boron atoms of Li[2H] are linked by a μ-H bridge. In the closely related molecule Li[3H], the corresponding μ-H atom can be abstracted with (Me 3 Si) 3 CLi to afford the B-B-bonded conjugated base Li 2 [3] (THF, 150 °C; 15 %). Li[1H] and Li[2H] were characterized by NMR spectroscopy and X-ray crystallography. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved luminescence properties of MoS2 monolayers grown via MOCVD: role of pre-treatment and growth parameters

NASA Astrophysics Data System (ADS)

Andrzejewski, D.; Marx, M.; Grundmann, A.; Pfingsten, O.; Kalisch, H.; Vescan, A.; Heuken, M.; Kümmell, T.; Bacher, G.

2018-07-01

Fabrication of transition metal dichalcogenides (TMDCs) via metalorganic chemical vapor deposition (MOCVD) represents one of the most attractive routes to large-scale 2D material layers. Although good homogeneity and electrical conductance have been reported recently, the relation between growth parameters and photoluminescence (PL) intensity—one of the most important parameters for optoelectronic applications—has not yet been discussed for MOCVD TMDCs. In this work, MoS2 is grown via MOCVD on sapphire (0001) substrates using molybdenum hexacarbonyl (Mo(CO)6, MCO) and di-tert-butyl sulphide as precursor materials. A prebake step under H2 atmosphere combined with a reduced MCO precursor flow increases the crystal grain size by one order of magnitude and strongly enhances PL intensity with a clear correlation to the grain size. A decrease of the linewidth of both Raman resonances and PL spectra down to full width at half maxima of 3.2 cm‑1 for the E 2g Raman mode and 60 meV for the overall PL spectrum indicate a reduced defect density at optimized growth conditions.

Protonation at the aromatic ring vs at the carbonyl group of lanthanide-diaryl ketone dianion species by aryl alcohols. Formation, structural characterization, and reactivity of lanthanide aryloxide, mixed aryloxide/alkoxide, and aryloxide/enolate complexes

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

Yoshimura, Takashi; Hou, Z.; Wakatsuki, Yasua

1995-11-01

Reaction of the ytterbium-benzophenone dianion complex (1), which was formed by reaction of Yb metal with benzophenone in THF/HMPA, with 2,6-di-tert-butyl-4-methylphenol, yielded the ytterbium(II) aryloxide complex Yb(OAr){sub 2}(HMPA){sub 2} (2, Ar= C{sub 6}H{sub 2} -{sup t}Bu{sub 2}-2,6-Me-4) as a major product (80%) and the ytterbium(III) enolate complex (3) as a minor one (ca. 5% yield). The mechanisms of these reactions are discussed. X-ray crystallographic studies reveal that 3, 4a, and 7b are isostructural, and so are 5a and 6. The central metal ions in these complexes are all five-coordinated in a trigonal bipyramid form (highly distorted in the case ofmore » 5a and 6) with two HMPA ligands at the apical and three anionic oxygen ligands at the equatorial positions. 25 refs., 7 figs., 7 tabs.« less

Time- and temperature-dependent migration studies of Irganox 1076 from plastics into foods and food simulants.

PubMed

Beldì, G; Pastorelli, S; Franchini, F; Simoneau, C

2012-01-01

The study provides an exhaustive set of migration data for octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076) from low-density polyethylene (LDPE) in several food matrices. Irganox 1076 was used as a model migrant because it represents one of the typical substances used as an antioxidant in food packaging polymers. Kinetic (time-dependent) migration studies of Irganox 1076 were performed for selected foodstuffs chosen with different physical-chemical properties and in relation to the actual European food consumption market. The effect of fat content and of the temperature of storage on the migration from plastic packaging was evaluated. The results show that migration increased with fat content and storage temperature. All data obtained from real foods were also compared with data obtained from simulants tested in the same conditions. In all studied cases, the kinetics in simulants were higher than those in foodstuffs. The work provides data valuable for the extension of the validation of migration model developed on simulants to foodstuffs themselves.

Effects of countercations on the structures and redox and spectroscopic properties of diruthenium catecholate complexes with ligand-unsupported Ru-Ru bonds.

PubMed

Chang, Ho-Chol; Mochizuki, Katsunori; Kitagawa, Susumu

2005-05-30

The molecular structures and physicochemical properties of diruthenium complexes with ligand-unsupported Ru-Ru bonds, generally formulated as [A2{Ru2(DTBCat)4}] (DTB = 3,5- or 3,6-di-tert-butyl; Cat(2-) = catecholate), were studied in detail by changing the countercations. First, the binding structures of the cations in a family of [{A(DME)n}2{Ru2(3,5-DTBCat)4}] (n = 2 for A+ = Li+ and Na+ and n = 1 for A+ = K+ and Rb+) were systematically examined to reveal the effects of the cations on the molecular structures and electrochemical properties. Second, the complex (n-Bu4N)2[Ru2(3,6-DTBCat)4] with a cation-free structure was synthesized using tetra-n-butylammonium cations. The complex clearly demonstrates first that the ligand-unsupported Ru-Ru bonds are essentially stabilized by the dianionic nature of the catecholate derivatives without any other bridging or supporting species. In contrast, the redox potentials and absorption spectra of the complexes can sensitively respond to the countercations depending upon the polarity of the solvents.