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Sample records for alkyl silica microcolumn

  1. Stability of inorganic mercury and methylmercury on yeast-silica gel microcolumns: field sampling capabilities

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Corona, M. [Universidad Complutense de Madrid (Spain). Dept. de Quimica Analitica

    2000-11-01

    The stability of methylmercury and inorganic mercury retained on yeast-silica gel microcolumns was established and compared with the stability of these species in solution. Yeast-silica gel columns with the retained analytes were stored for two months at three different temperatures: -20 C, 4 C and room temperature. At regular time intervals, both mercury species were eluted and quantified by cold vapor atomic absorption spectrometry (CVAAS). Methylmercury was found stable in the columns over the two-month period at the three different temperatures tested while the concentration of inorganic mercury decreased after one week's storage even at -20 C. These results are of great interest since the use of these microcolumns allows the preconcentration and storage of mercury species until analysis, thus saving laboratory space and avoiding the problems associated with maintaining species integrity in aqueous solution. (orig.)

  2. Low energy microcolumn for large field view inspection

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Chul [Department of Optometry, Eulji University, 212 Yangji-dong, Sujeong-gu, Seongnam-si, Gyeonggi-do 461-713 (Korea, Republic of); Ahn, Seung-Joon; Oh, Tae-Sik; Kim, Dae-Wook [Department of Nanoscience, Sun Moon University 100 Kalsan-ri, Tangjeong-myun, Asan-si, Chungnam 336-708 (Korea, Republic of); Kim, Ho-Seob, E-mail: hskim3@sunmoon.ac.kr [Department of Nanoscience, Sun Moon University 100 Kalsan-ri, Tangjeong-myun, Asan-si, Chungnam 336-708 (Korea, Republic of); Jang, Won Kweon [Division of Electronic, Computer and Communication Engineering, Hanseo University 360 DaeKook-ri, Haemi-myun, Seosan-si, Chungnam 356-706 (Korea, Republic of)

    2011-12-15

    Since the development of microcolumn system, it attracted much attention because multiple microcolumns can be assembled into arrayed form, which is expected to generate multiple electron beams and overcome the disadvantage of electron beam inspection equipments, low throughput . However, it is not easy to apply a microcolumn to the practical inspection or testing equipment since its scanning area is too small. Even if the arrayed operation using multiple microcolumns can overcome this limit, it requires complicated supporting systems and related technologies to operate a number of microcolumns simultaneously. Therefore, we tried to modify microcolumn design itself so that it can have a large field of view. In this work, two kinds of modified columns will be suggested and the preliminary results showing their performance of scanning large area will be discussed. -- Highlights: Black-Right-Pointing-Pointer Two types of microcolumn designs to achieve a large field of view are fabricated. Black-Right-Pointing-Pointer Field of view of a microcolumn increases linearly with the working distance. Black-Right-Pointing-Pointer New designed microcolumns can be developed as a low energy column system for large view inspections.

  3. Alumina/silica aerogel with zinc chloride as an alkylation catalyst

    Directory of Open Access Journals (Sweden)

    DEJAN U. SKALA

    2001-10-01

    Full Text Available The alumina/silica with zinc chloride aerogel alkylation catalyst was obtained using a one step sol-gel synthesis, and subsequent drying with supercritical carbon dioxide. The aerogel catalyst activity was found to be higher compared to the corresponding xerogel catalyst, as a result of the higher aerogel surface area, total pore volume and favourable pore size distribution. Mixed Al–O–Si bonds were present in both gel catalyst types. Activation by thermal treatment in air was needed prior to catalytic alkylation, due to the presence of residual organic groups on the aerogel surface. The optimal activation temperature was found to be in the range 185–225°C, while higher temperatures resulted in the removal of zinc chloride from the surface of the aerogel catalyst with a consequential decrease in the catalytic activity. On varying the zinc chloride content, the catalytic activity of the aerogel catalyst exhibited a maximum. High zinc chloride contents decreased the catalytic activity of the aerogel catalyst as the result of the pores of the catalyst being plugged with this compound, and the separation of the alumina/silica support into Al-rich and Si-rich phases. The surface area, total pore volume, pore size distribution and zinc chloride content had a similar influence on the activity of the aerogel catalyst as was the case of xerogel catalyst and supported zinc chloride catalysts.

  4. Role of alkyl alcohol on viscosity of silica-based chemical gels for decontamination of highly radioactive nuclear facilities

    International Nuclear Information System (INIS)

    Choi, B. S.; Yoon, S. B.; Jung, C. H.; Lee, K. W.; Moon, J. K.

    2012-01-01

    Silica-based chemical gel for the decontamination of nuclear facilities was prepared by using fumed silica as a viscosifier, a 0.5 M Ce (IV) solution dissolved in concentrated nitric acid as a chemical decontamination agent, and tripropylene glycol butyl ether (TPGBE) as a co-viscosifier. A new effective strategy for the preparation of the chemical gel was investigated by introducing the alkyl alcohols as organic solvents to effectively dissolve the co-viscosifier. The mixture solution of the co-viscosifier and alkyl alcohols was more effective in the control of viscosity than that of the co-viscosifier only in gel. Here, the alkyl alcohols played a key role as an effective dissolution solvent for the co-viscosifier in the preparation of the chemical gel, resulting in a reducing of the amount of the co-viscosifier and gel time compared with that of the chemical gel prepared without the alkyl alcohols. It was considered that the alkyl alcohols contributed to the effective dissolution of the co-viscosifier as well as the homogeneous mixing in the formation of the gel, while the co-viscosifier in an aqueous media of the chemical decontamination agent solution showed a lower solubility. The decontamination efficiency of the chemical gels prepared in this work using a multi-channel analyzer (MCA) showed a high decontamination efficiency of over ca. 94% and ca. 92% for Co-60 and Cs-137 contaminated on surface of the stainless steel 304, respectively. (authors)

  5. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas; Le Qué mé ner, Fré dé ric; Bouhoute, Yassine; Szeto, Kai C.; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja; Delevoye, Laurent; Gauvin, Ré gis M.; Taoufik, Mostafa; Basset, Jean-Marie

    2016-01-01

    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  6. Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

    KAUST Repository

    Merle, Nicolas

    2016-12-05

    The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

  7. Microcolumns with self-assembled particle frits for proteomics

    DEFF Research Database (Denmark)

    Ishihama, Yasushi; Rappsilber, Juri; Andersen, Jens S

    2002-01-01

    LC-MS-MS experiments in proteomics are usually performed with packed microcolumns employing frits or outlets smaller than the particle diameter to retain the packing material. We have developed packed microcolumns using self-assembled particles (SAPs) as frits that are smaller than the size...... of the outlet. A five to one ratio of outlet size to particle diameter appears to be the upper maximum. In these situations the particles assembled into an arch over the outlet like the stones in a stone bridge. When 3 microm particles were packed into a tapered column with an 8 microm outlet, two particles...

  8. Silica coated ionic liquid templated mesoporous silica nanoparticles ...

    African Journals Online (AJOL)

    A series of long chain pyridinium based ionic liquids 1-tetradecylpyridinium bromide, 1-hexadecylpyridinium bromide and 1-1-octadecylpyridinium bromide were used as templates to prepare silica coated mesoporous silica nanoparticles via condensation method under basic condition. The effects of alkyl chain length on ...

  9. Application of a Heterogeneous Chiral Titanium Catalyst Derived from Silica-Supported 3-Aryl H8-BINOL to Enantioselective Alkylation and Arylation of Aldehydes.

    Science.gov (United States)

    Akai, Junichiro; Watanabe, Satoshi; Michikawa, Kumiko; Harada, Toshiro

    2017-07-07

    A 3-aryl H 8 -BINOL was grafted on the surface of silica gel using a hydrosilane derivative as a precursor, and the resulting silica-supported ligand (6 mol %) was employed in the enantioselective alkylation and arylation of aldehydes in the presence of Ti(O i Pr) 4 . The reactions using Et 2 Zn, Et 3 B, and aryl Grignard reagents all afforded the corresponding adducts in high enantioselectivities and yields. The silica-immobilized titanium catalyst could be reused up to 14 times without appreciable deterioration of the activity.

  10. Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis

    KAUST Repository

    Hamieh, Ali Imad Ali

    2016-07-28

    An efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.

  11. Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis

    KAUST Repository

    Hamieh, Ali Imad Ali; Dey, Raju; Samantaray, Manoja; Abdel-Azeim, Safwat; Abou-Hamad, Edy; Chen, Yin; Pelletier, Jeremie; Cavallo, Luigi; Basset, Jean-Marie

    2016-01-01

    An efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.

  12. Modified mesoporous silica materials for on-line separation and preconcentration of hexavalent chromium using a microcolumn coupled with flame atomic absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Wang Zheng, E-mail: wangzheng@mail.sic.ac.cn [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Fang Dongmei; Li Qing [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); East China University of Science and Technology, Shanghai 200237 (China); Zhang Lingxia; Qian Rong; Zhu Yan; Qu Haiyun [Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050 (China); Du Yiping [East China University of Science and Technology, Shanghai 200237 (China)

    2012-05-06

    Highlights: Black-Right-Pointing-Pointer A modified SBA-15 mesoporous silica material (NH{sub 2}-SBA-15) was synthesized as sorbent. Black-Right-Pointing-Pointer The material was used for the first time in a flow injection on-line solid phase extraction (SPE) coupled with flame atomic absorption spectrometry (FAAS) to detect trace Cr (VI). Black-Right-Pointing-Pointer The NH{sub 2}-SBA-15 enables retain Cr (VI) with an enrichment factor of 44. Black-Right-Pointing-Pointer The micro-column of NH{sub 2}-SBA-15 underwent more than 100 adsorption/desorption cycles. - Abstract: A modified SBA-15 mesoporous silica material NH{sub 2}-SBA-15 was synthesized successfully by grafting {gamma}-aminopropyl-triethoxysilane. The material was characterized using transmission electron microscopy (TEM) and Fourier transform infrared/Raman (FT-IR/Raman) spectroscopy, and used for the first time in a flow injection on-line solid phase extraction (SPE) coupled with flame atomic absorption spectrometry (FAAS) to detect trace Cr (VI). Effective sorption of Cr (VI) was achieved at pH 2.0 with no interference from Cr (III) and other ions and 0.5 mol L{sup -1} NH{sub 3}{center_dot}H{sub 2}O solution was found optimal for the complete elution of Cr (VI). An enrichment factor of 44 and was achieved under optimized experimental conditions at a sample loading of 2.0 mL min{sup -1} sample loading (300 s) and an elution flow rate of 2.0 mL min{sup -1} (24 s). The precision of the 11 replicate Cr (VI) measurements was 2.1% at the 100 {mu}g L{sup -1} level with a detection limit of 0.2 {mu}g L{sup -1} (3 s, n = 10) using the FAAS. The developed method was successfully applied to trace chromium determination in waste water. The accuracy was validated using a certified reference material of riverine water (GBW08607).

  13. Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

    KAUST Repository

    Merle, Nicolas

    2017-09-25

    A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

  14. Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

    KAUST Repository

    Merle, Nicolas; Le Qué mé ner, Fré dé ric; Barman, Samir; Samantaray, Manoja; Szeto, Kai C.; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

    2017-01-01

    A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

  15. Fabrication of a micrometer Ni–Cu alloy column coupled with a Cu micro-column for thermal measurement

    International Nuclear Information System (INIS)

    Lin, J C; Chang, T K; Yang, J H; Jeng, J H; Lee, D L; Jiang, S B

    2009-01-01

    Micrometer Ni–Cu alloy columns have been fabricated by the micro-anode-guided electroplating (MAGE) process in the citrate bath. The surface morphology and chemical composition of the micro-columns were determined by copper concentration in the bath and by the electrical bias of MAGE. When fabricated in a bath of dilute copper (i.e. 4 mM) at lower voltages (e.g. 3.8 and 4.0 V), the alloy micro-columns revealed uniform diameter and smooth appearance. The alloy composition demonstrated an increase in the wt% ratio of Ni/Cu from 75/25, 80/20, 83/17 to 87/13 with increasing electrical bias from 3.8, 4.0, 4.2 to 4.4 V. However, it decreases from 75/25, 57/43 to 47/53 with increasing copper concentration from 4, 8 to 12 mM in the bath. Citrate plays a role in forming complexes with nickel and copper at similar reduction potentials, thus reducing simultaneously to Ni–Cu alloy. The mechanism for fabricating alloy micro-columns could be delineated on the basis of cathodic polarization of the complexes. A couple of micro-columns were fabricated using MAGE in constructing a pure copper micro-column on the top of a Ni/Cu (at 47/53) alloy micro-column. This micro-thermocouple provides a satisfactory measurement with good sensitivity and precision

  16. Photocatalytic and photoelectrochemical performance of Ta{sub 3}N{sub 5} microcolumn films fabricated using facile reactive sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Der-Hwa [Department of Materials Science and Engineering, National Cheng Kung University, No. 1 University Road, Tainan City 70101, Taiwan (China); Chang, Kao-Shuo, E-mail: kschang@mail.ncku.edu.tw [Department of Materials Science and Engineering, National Cheng Kung University, No. 1 University Road, Tainan City 70101, Taiwan (China); Promotion Center for Global Materials Research, National Cheng Kung University, No. 1 University Road, Tainan City 70101, Taiwan (China)

    2016-08-21

    This paper presents the photocatalytic and photoelectrochemical (PEC) properties of Ta{sub 3}N{sub 5} microcolumn films. The highlights include (1) overcoming the fundamental barrier of standard reactive sputtering for fabricating microcolumns; (2) preventing unnecessary complexity from complicating facile sputtering; (3) an alternative but effective approach for fabricating Ta{sub 3}N{sub 5} without using caustic NH{sub 3} gases; (4) investigating morphology tuning for favorable photocatalysis and PEC reactions; and (5) elucidating the relationships of the structures, morphologies, and properties of Ta{sub 3}N{sub 5} microcolumns. High-resolution transmission electron microscopy and selective-area electron diffraction verified the polycrystallinity of Ta{sub 3}N{sub 5} microcolumns, of which the elemental compositions and stoichiometry were measured using electron-probe energy dispersive spectroscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy. The corresponding band gap was determined to be approximately 2.1 eV. The sample exhibited a superior photodegradation capability; the photodegradation rate constant k was determined to be approximately 1.4 times higher than that of P25 under UV irradiation. A photocatalytic and PEC cycling test indicated the photodegradation reusability and photostability of the Ta{sub 3}N{sub 5} microcolumns. The incident photon-to-current efficiency performance reached 6%, suggesting that these microcolumns hold potential for application in PEC devices.

  17. Optimization of electrostatic lens systems for low-energy scanning microcolumn applications

    International Nuclear Information System (INIS)

    Oh, Tae-Sik; Kim, Dae-Wook; Ahn, Seungjoon; Kim, Young Chul; Kim, Ho-Seob; Ahn, Seong Joon

    2008-01-01

    The optimization of a low-energy scanning microcolumn is proposed by adopting a modified Einzel lens sandwiched between an aligner and a deflector. The modified Einzel lens is composed of four electrodes, and the two center electrodes are specially designed quadrupole lenses having keyhole type rather than circular apertures. The outer electrodes of the Einzel lens having circular apertures are grounded, and the quadrupole lens is operated by applying the quadrupole voltages. The effects of the separated deflector system and the static quadrupole lens were investigated by analyzing the scanning electron beam spot at the target, and the results show that the proposed system can improve the performance of the scanning microcolumn

  18. A new microcolumn-type microchip for examining the expression of chimeric fusion genes using a nucleic acid sandwich hybridization technique.

    Science.gov (United States)

    Ohnishi, Michihiro; Sasaki, Naoyuki; Kishimoto, Takuya; Watanabe, Hidetoshi; Takagi, Masatoshi; Mizutani, Shuki; Kishii, Noriyuki; Yasuda, Akio

    2014-11-01

    We report a new type of microcolumn installed in a microchip. The architecture allows use of a nucleic acid sandwich hybridization technique to detect a messenger RNA (mRNA) chain as a target. Data are presented that demonstrate that the expression of a chimeric fusion gene can be detected. The microcolumn was filled with semi-transparent microbeads made of agarose gel that acted as carriers, allowing increased efficiency of the optical detection of fluorescence from the microcolumn. The hybrid between the target trapped on the microbeads and a probe DNA labeled with a fluorescent dye was detected by measuring the intensity of the fluorescence from the microcolumn directly. These results demonstrate an easy and simple method for determining the expression of chimeric fusion genes with no preamplification. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Development of the first well-defined tungsten oxo alkyl derivatives supported on silica by SOMC: towards a model of WO3/SiO2 olefin metathesis catalyst

    KAUST Repository

    Mazoyer, Etienne; Merle, Nicolas; Mallmann, Aimery De; Basset, Jean-Marie; Berrier, Elise; Delevoye, Laurent; Paul, Jean Franois; Nicholas, Christopher P.; Gauvin, Ré gis M.; Taoufik, Mostafa

    2010-01-01

    A well-defined, silica-supported tungsten oxo alkyl species prepared by the surface organometallic chemistry approach displays high and sustained activity in propene metathesis. Remarkably, its catalytic performances outpace those of the parent imido derivative, underlining the importance of the oxo ligand in the design of robust catalysts. © 2010 The Royal Society of Chemistry.

  20. Effects of Na and K ions on the crystallization of low-silica X zeolite and its catalytic performance for alkylation of toluene with methanol

    Energy Technology Data Exchange (ETDEWEB)

    Hui, Haitao; Gao, Junhua; Wang, Gencun; Liu, Ping; Zhang, Kan, E-mail: gaojunhua@sxicc.ac.cn, E-mail: zhangkan@sxicc.ac.cn [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan (China)

    2014-01-15

    The crystallization of low-silica X zeolite (LSX) was studied in Na-K gel systems with different extents of replacement of Na by K while fixed content of other components. X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, infrared spectra, and nuclear magnetic resonance were used to characterize liquid and solid phase. In the synthesis of LSX, the molar ratio of K/(Na + K) affects the crystallization and the composition of final products. A higher mole fraction of K corresponded to a lower crystallization rate, higher concentration of Si in the liquid phase, and lower Si/Al ratio of the obtained LSX. The average size of LSX products steadily increased with the progressive replacement of Na by K in the initial gels, and crystal morphology of the LSX products gradually changed from round to octahedral. For alkylation of toluene with methanol over obtained LSX, the selectivity of ring alkylation product xylene decreased while the side chain alkylation products styrene and ethylbenzene increased with the increased x values except x = 0, which was due to its low crystallinity. (author)

  1. Effects of Na and K ions on the crystallization of low-silica X zeolite and its catalytic performance for alkylation of toluene with methanol

    International Nuclear Information System (INIS)

    Hui, Haitao; Gao, Junhua; Wang, Gencun; Liu, Ping; Zhang, Kan

    2014-01-01

    The crystallization of low-silica X zeolite (LSX) was studied in Na-K gel systems with different extents of replacement of Na by K while fixed content of other components. X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, scanning electron microscopy, infrared spectra, and nuclear magnetic resonance were used to characterize liquid and solid phase. In the synthesis of LSX, the molar ratio of K/(Na + K) affects the crystallization and the composition of final products. A higher mole fraction of K corresponded to a lower crystallization rate, higher concentration of Si in the liquid phase, and lower Si/Al ratio of the obtained LSX. The average size of LSX products steadily increased with the progressive replacement of Na by K in the initial gels, and crystal morphology of the LSX products gradually changed from round to octahedral. For alkylation of toluene with methanol over obtained LSX, the selectivity of ring alkylation product xylene decreased while the side chain alkylation products styrene and ethylbenzene increased with the increased x values except x = 0, which was due to its low crystallinity. (author)

  2. Q Sepharose micro-column chromatography: A simple screening method for identifying beta thalassemia traits and hemoglobin E carriers.

    Science.gov (United States)

    Wong, Peerapon; Sritippayawan, Suchila; Suwannakhon, Narutchala; Tapprom, Akamon; Deoisares, Rawisut; Sanguansermsri, Torpong

    2016-11-01

    For beta thalassemia control program in pregnancy, mass screening of the carrier state by determination of the hemoglobin (Hb) A 2 and Hb E proportions and mutation analysis is a preferred method for making prenatal diagnoses. Q Sepharose micro-column chromatography, developed for the determination of Hb A 2 and Hb E for screening purposes, was compared with high performance liquid chromatography (HPLC) to ascertain its relative accuracy and reliability. Results using Q Sepharose micro-column chromatography in 350 blood specimens, including 50 samples genetically proven to be beta thalassemia heterozygotes, were compared to HPLC for validation. An additional study was conducted to test a clinical application on a large-scale survey for beta thalassemia in 1581 pregnant women and their spouses. The mean (±SD) Hb A 2 proportions in the normal and genetically proven beta thalassemia heterozygotes were 2.70±0.40% and 6.30±1.23%, respectively, as determined by Q-Sepharose micro-column chromatography, and 2.65±0.31% and 5.37±0.96%, respectively, as determined by HPLC. The mean Hb E proportions in the Hb E heterozygotes were 23.25±4.13% and 24.72±3.5% as determined by Q Sepharose micro-column chromatography and HPLC, respectively. In the large-scale survey for beta thalassemia, 23 at risk couples were detected. Seven affected fetuses were identified by prenatal diagnosis. Q Sepharose micro-column chromatography was found to be reliable, reproducible and well-suited for large-scale surveys. Additionally, by being reusable and convenient, this simple and economical chromatography method may be an alternative means to screen for beta thalassemia and Hb E carriers in the mass population. Copyright © 2016 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

  3. Analysis of drug-protein binding using on-line immunoextraction and high-performance affinity microcolumns: Studies with normal and glycated human serum albumin.

    Science.gov (United States)

    Matsuda, Ryan; Jobe, Donald; Beyersdorf, Jared; Hage, David S

    2015-10-16

    A method combining on-line immunoextraction microcolumns with high-performance affinity chromatography (HPAC) was developed and tested for use in examining drug-protein interactions with normal or modified proteins. Normal human serum albumin (HSA) and glycated HSA were used as model proteins for this work. High-performance immunoextraction microcolumns with sizes of 1.0-2.0 cm × 2.1mm i.d. and containing anti-HSA polyclonal antibodies were developed and tested for their ability to bind normal HSA or glycated HSA. These microcolumns were able to extract up to 82-93% for either type of protein at 0.05-0.10 mL/min and had a binding capacity of 0.34-0.42 nmol HSA for a 1.0 cm × 2.1mm i.d. microcolumn. The immunoextraction microcolumns and their adsorbed proteins were tested for use in various approaches for drug binding studies. Frontal analysis was used with the adsorbed HSA/glycated HSA to measure the overall affinities of these proteins for the drugs warfarin and gliclazide, giving comparable values to those obtained previously using similar protein preparations that had been covalently immobilized within HPAC columns. Zonal elution competition studies with gliclazide were next performed to examine the specific interactions of this drug at Sudlow sites I and II of the adsorbed proteins. These results were also comparable to those noted in prior work with covalently immobilized samples of normal HSA or glycated HSA. These experiments indicated that drug-protein binding studies can be carried out by using on-line immunoextraction microcolumns with HPAC. The same method could be used in the future with clinical samples and other drugs or proteins of interest in pharmaceutical studies or biomedical research. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Synthesis and application of silica gel modified with alkoxyalcohols. Alkoxyalcohol shushoku silica gel no gosei to riyo

    Energy Technology Data Exchange (ETDEWEB)

    Moriguchi, T.; Ishiguro, H.; Matsubara, Y.; Yoshihara, M.; Maeshima, T.; Ito, S. (Kinki University, Osaka (Japan). Faculty of Science and Engineering)

    1991-08-20

    Several kinds of silica gel modified by alkoxyalcohols were synthesized by refluxing and dehyration and the organic reactions were studied when these silica gels were used as the catalyst. It could be confirmed by FT-IR spectra, DTA and elementary analysis that alkoxylalcohols adhere to the surface of silica gels without any decomposition. The acetate was produced by using alkyl halides. It was found that the modified silica gels had clearly the catalytic action for the reaction with n-hexyl bromide and dibromoethane although unmodified silica gels did not show the catalytic action. The reducing reaction of carbonyl compounds was carried out. The reaction proceeded at 25 centigrade for acetophenone, cyclohexanone, 1-indanone and 2-octanone to produce the corresponding reduction products. 11 refs., 5 figs., 4 tabs.

  5. Quaternary ammonium-functionalized silica sorbents for the solid-phase extraction of aromatic amines under normal phase conditions.

    Science.gov (United States)

    Vidal, Lorena; Robin, Orlane; Parshintsev, Jevgeni; Mikkola, Jyri-Pekka; Riekkola, Marja-Liisa

    2013-04-12

    Quaternary ammonium-functionalized silica materials were synthesized and applied for solid-phase extraction (SPE) of aromatic amines, which are classified as priority pollutants by US Environmental Protection Agency. Hexamethylenetetramine used for silica surface modification for the first time was employed as SPE sorbent under normal phase conditions. Hexaminium-functionalized silica demonstrated excellent extraction efficiencies for o-toluidine, 4-ethylaniline and quinoline (recoveries 101-107%), while for N,N-dimethylaniline and N-isopropylaniline recoveries were from low to moderate (14-46%). In addition, the suitability of 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica as SPE sorbent was tested under normal phase conditions. The recoveries achieved for the five aromatic amines ranged from 89 to 99%. The stability of the sorbent was evaluated during and after 150 extractions. Coefficients of variation between 4.5 and 10.2% proved a high stability of the synthesized sorbent. Elution was carried out using acetonitrile in the case of hexaminium-functionalized silica and water for 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent. After the extraction the analytes were separated and detected by liquid chromatography ultraviolet detection (LC-UV). The retention mechanism of the materials was primarily based on polar hydrogen bonding and π-π interactions. Comparison made with activated silica proved the quaternary ammonium-functionalized materials to offer different selectivity and better extraction efficiencies for aromatic amines. Finally, 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent was successfully tested for the extraction of wastewater and soil samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Nanophotonic production, modulation and switching of ions by silicon microcolumn arrays

    Science.gov (United States)

    Vertes, Akos; Walker, Bennett N.

    2013-09-10

    The production and use of silicon microcolumn arrays that harvest light from a laser pulse to produce ions are described. The systems of the present invention seem to behave like a quasi-periodic antenna array with ion yields that show profound dependence on the plane of laser light polarization and the angle of incidence. By providing photonic ion sources, this enables enhanced control of ion production on a micro/nano scale and direct integration with miniaturized analytical devices.

  7. Aminopropyl-Silica Hybrid Particles as Supports for Humic Acids Immobilization

    Directory of Open Access Journals (Sweden)

    Mónika Sándor

    2016-01-01

    Full Text Available A series of aminopropyl-functionalized silica nanoparticles were prepared through a basic two step sol-gel process in water. Prior to being aminopropyl-functionalized, silica particles with an average diameter of 549 nm were prepared from tetraethyl orthosilicate (TEOS, using a Stöber method. In a second step, aminopropyl-silica particles were prepared by silanization with 3-aminopropyltriethoxysilane (APTES, added drop by drop to the sol-gel mixture. The synthesized amino-functionalized silica particles are intended to be used as supports for immobilization of humic acids (HA, through electrostatic bonds. Furthermore, by inserting beside APTES, unhydrolysable mono-, di- or trifunctional alkylsilanes (methyltriethoxy silane (MeTES, trimethylethoxysilane (Me3ES, diethoxydimethylsilane (Me2DES and 1,2-bis(triethoxysilylethane (BETES onto silica particles surface, the spacing of the free amino groups was intended in order to facilitate their interaction with HA large molecules. Two sorts of HA were used for evaluating the immobilization capacity of the novel aminosilane supports. The results proved the efficient functionalization of silica nanoparticles with amino groups and showed that the immobilization of the two tested types of humic acid substances was well achieved for all the TEOS/APTES = 20/1 (molar ratio silica hybrids having or not having the amino functions spaced by alkyl groups. It was shown that the density of aminopropyl functions is low enough at this low APTES fraction and do not require a further spacing by alkyl groups. Moreover, all the hybrids having negative zeta potential values exhibited low interaction with HA molecules.

  8. Determination of trace lithium in uranium compounds by adsorption on activated alumina using a micro-column method.

    Science.gov (United States)

    Luo, Ming-Biao; Li, Bo-Ping; Yang, Zhi; Liu, Wei; Sun, Yu-Zhen

    2008-08-01

    A novel method using a micro-column packed with active alumina as solid phase was proposed for separation of trace lithium from uranium compounds prior to determination. The method is based on a preliminary chromatographic separation of the total amount of uranium. This separation involves passing the solution containing sodium carbonate through active alumina and then eluting the trace lithium retained by the solid phase with a solution of sulfuric acid. Two modes, off-line and on-line micro-column preconcentration, were performed. In conjunction with atomic absorption spectrometry, this on-line preconcentration technique allows a determination of lithium at 10(-9) level. Both off-line and on-line mode operation conditions were investigated in separation and determination of trace lithium by micro-column method (length of column bed, flow rate, etc.). The adsorption capacity of activated alumina was found to be 343 microg g(-1) for lithium. Under the optimal operation condition, the detection limit (DL) of on-line preconcentration corresponding to three times the standard deviation of the blank (S/N = 3) was found to be 1.3 ng mL(-1) and the RSD of this method is 3.32% (n = 5). The on-line calibration graph was linear over the range 20 - 200 ng mL(-1). A good preconcentration factor 820 was achieved by experiment under the on-line mode. The developed method was applied to the analysis of trace lithium in nuclear grade uranium compounds.

  9. Alkylation of isobutane by butenes on zirconium sulfate catalysts

    International Nuclear Information System (INIS)

    Lavrenov, A.V.; Perelevskij, E.V.; Finevich, V.P.; Zajkovskij, V.I.; Paukshtis, E.A.; Duplyakiv, V.K.; Bal'zhinimaev, B.S.

    2003-01-01

    Preparation of applied zirconium sulfate catalysts obtained by the method of impregnation is investigated. Results of comparative study of structural, acid-base and catalytic properties of sulfated zirconium dioxide applied on silica gel and aluminium oxide are represented. Intervals of values of synthesis basic parameters and characteristics of catalysts properties providing achievement of high activity and selectivity in isobutane alkylation by butenes in liquid phase are determined [ru

  10. Synthesis and Performance of a Biomimetic Indicator for Alkylating Agents.

    Science.gov (United States)

    Provencher, Philip A; Love, Jennifer A

    2015-10-02

    4-(4-Nitrobenzyl)pyridine (NBP) is a colorimetric indicator compound for many types of carcinogenic alkylating agents. Because of the similar reactivity of NBP and guanine in DNA, NBP serves as a DNA model. NBP assays are used in the toxicological screening of pharmaceutical compounds, detection of chemical warfare agents, environmental hygiene technology, preliminary toxicology tests, mutagenicity of medicinal compounds, and other chemical analyses. Nevertheless, the use of NBP as a DNA model suffers from the compound's low water solubility, its lack of reactive oxygen sites, and dissimilar steric encumbrance compared to DNA. We report herein the design and synthesis of NBP derivatives that address some of these issues. These derivatives have been tested in solution and found to be superior in the colorimetric assay of the alkylating anticancer drug cyclophosphamide. The derivatives have also been integrated into a polymeric silica material which changes color upon the exposure to dangerous alkylating agents, such as iodomethane vapor, without the need for an exogenous base. This material modernizes the NBP assay from a time-consuming laboratory analysis to a real-time solid state sensor, which requires neither solvent nor additional reagents and can detect both gas- and solution-phase alkylating agents.

  11. Laser desorption ionization and peptide sequencing on laser induced silicon microcolumn arrays

    Science.gov (United States)

    Vertes, Akos [Reston, VA; Chen, Yong [San Diego, CA

    2011-12-27

    The present invention provides a method of producing a laser-patterned silicon surface, especially silicon wafers for use in laser desorption ionization (LDI-MS) (including MALDI-MS and SELDI-MS), devices containing the same, and methods of testing samples employing the same. The surface is prepared by subjecting a silicon substrate to multiple laser shots from a high-power picosecond or femtosecond laser while in a processing environment, e.g., underwater, and generates a remarkable homogenous microcolumn array capable of providing an improved substrate for LDI-MS.

  12. Nitriles at Silica Interfaces Resemble Supported Lipid Bilayers.

    Science.gov (United States)

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

    2016-09-20

    Nitriles are important solvents not just for bulk reactions but also for interfacial processes such as separations, heterogeneous catalysis, and electrochemistry. Although nitriles have a polar end and a lipophilic end, the cyano group is not hydrophilic enough for these substances to be thought of as prototypical amphiphiles. This picture is now changing, as research is revealing that at a silica surface nitriles can organize into structures that, in many ways, resemble lipid bilayers. This unexpected organization may be a key component of unique interfacial behavior of nitriles that make them the solvents of choice for so many applications. The first hints of this lipid-bilayer-like (LBL) organization of nitriles at silica interfaces came from optical Kerr effect (OKE) experiments on liquid acetonitrile confined in the pores of sol-gel glasses. The orientational dynamics revealed by OKE spectroscopy suggested that the confined liquid is composed of a relatively immobile sublayer of molecules that accept hydrogen bonds from the surface silanol groups and an interdigitated, antiparallel layer that is capable of exchanging into the centers of the pores. This picture of acetonitrile has been borne out by molecular dynamics simulations and vibrational sum-frequency generation (VSFG) experiments. Remarkably, these simulations further indicate that the LBL organization is repeated with increasing disorder at least 20 Å into the liquid from a flat silica surface. Simulations and VSFG and OKE experiments indicate that extending the alkyl chain to an ethyl group leads to the formation of even more tightly packed LBL organization featuring entangled alkyl tails. When the alkyl portion of the molecule is a bulky t-butyl group, packing constraints prevent well-ordered LBL organization of the liquid. In each case, the surface-induced organization of the liquid is reflected in its interfacial dynamics. Acetonitrile/water mixtures are favored solvent systems for separations

  13. Micro-column plasma emission liquid chromatograph. [Patent application

    Science.gov (United States)

    Gay, D.D.

    1982-08-12

    In a direct current plasma emission spectrometer for use in combination with a microcolumn liquid chromatograph, an improved plasma source unit is claimed. The plasma source unit includes a quartz capillary tube having an inlet means, outlet off gas means and a pair of spaced electrodes defining a plasma region in the tube. The inlet means is connected to and adapted to receive eluant of the liquid chromatograph along with a stream of plasma-forming gas. There is an opening through the wall of the capillary tube penetrating into the plasma region. A soft glass capillary light pipe is disposed at the opening, is connected to the spectrometer, and is adapted to transmit light passing from the plasma region to the spectrometer. There is also a source of electromotive force connected to the electrodes sufficient to initiate and sustain a plasma in the plasma region of the tube.

  14. Dendrimer-Stabilized Ru Nanoparticles Immobilized in Organo-Silica Materials for Hydrogenation of Phenols

    Directory of Open Access Journals (Sweden)

    Eduard Karakhanov

    2017-03-01

    Full Text Available New hybrid catalysts based on Ru nanoparticles, encapsulated into poly(propylene imine dendrimers, immobilized into silica pores, were synthesized and examined for the hydrogenation of alkyl-substituted phenols. The corresponding alkyl-substituted cyclohexanols were presented as the major reaction products, while incomplete hydrogenation products appeared to be minor. A competition between the sterical factors of dendrimer-containing carriers and the electronic factors of substrate substituents influenced the hydrogenation rate of the alkyl-substituted phenols. The carrier structure was found to have a significant influence on both the physical and chemical properties of the catalysts and their hydrogenation activity. The synthesized hybrid catalysts appeared to be stable after recycling and could be re-used several times without significant loss of activity.

  15. Heterofacial alkylation of alkylenediamines by higher alkyl halides

    International Nuclear Information System (INIS)

    Semenov, V.A.; Kryshko, G.M.; Sokal'skaya, L.I.; Zhukova, N.G.

    1985-01-01

    A study of the physiochemical properties of alkylenediamines substituted by lower alkyls, showed that they possess increased complex-forming ability with respect to salts of different metals as titanium, niobium, zirconium, molybdenum, and zinc. To create a simpler method of synthesis of higher tetraaklyalkylalklyenediamines, based on the use of the accessible domestic raw material, the authors investigated the reaction of alkylenediamines with various alkyl halides. It was established that the best reagents can be obtained using alkyl bromides. It is concluded that the procedure of alkylation of alkylenediamines by higher alkyl halides in the presence of water developed permits the production of terraalkylalkylenediamines in one step with good yield and with purity acceptable for use as extraction reagents

  16. Laser desorption/ionization from nanostructured surfaces: nanowires, nanoparticle films and silicon microcolumn arrays

    International Nuclear Information System (INIS)

    Chen Yong; Luo Guanghong; Diao Jiajie; Chornoguz, Olesya; Reeves, Mark; Vertes, Akos

    2007-01-01

    Due to their optical properties and morphology, thin films formed of nanoparticles are potentially new platforms for soft laser desorption/ionization (SLDI) mass spectrometry. Thin films of gold nanoparticles (with 12±1 nm particle size) were prepared by evaporation-driven vertical colloidal deposition and used to analyze a series of directly deposited polypeptide samples. In this new SLDI method, the required laser fluence for ion detection was equal or less than what was needed for matrix-assisted laser desorption/ionization (MALDI) but the resulting spectra were free of matrix interferences. A silicon microcolumn array-based substrate (a.k.a. black silicon) was developed as a new matrix-free laser desorption ionization surface. When low-resistivity silicon wafers were processed with a 22 ps pulse length 3xω Nd:YAG laser in air, SF 6 or water environment, regularly arranged conical spikes emerged. The radii of the spike tips varied with the processing environment, ranging from approximately 500 nm in water, to ∼2 μm in SF 6 gas and to ∼5 μm in air. Peptide mass spectra directly induced by a nitrogen laser showed the formation of protonated ions of angiotensin I and II, substance P, bradykinin fragment 1-7, synthetic peptide, pro14-arg, and insulin from the processed silicon surfaces but not from the unprocessed areas. Threshold fluences for desorption/ionization were similar to those used in MALDI. Although compared to silicon nanowires the threshold laser pulse energy for ionization is significantly (∼10x) higher, the ease of production and robustness of microcolumn arrays offer complementary benefits

  17. Early Stages of Pulsed-Laser Growth of Silicon Microcolumns and Microcones in Air and SF6

    International Nuclear Information System (INIS)

    Fowlkes, J.D.; Lowndes, D.H.; Pedraza, A.J.

    1999-01-01

    Dense arrays of high-aspect-ratio silicon microcolumns and microcones are formed by cumulative nanosecond pulsed excimer laser irradiation of single-crystal silicon in oxidizing atmospheres such as air and SF 6 . Growth of such surface microstructures requires a redeposition model and also involves elements of self-organization. The shape of the microstructures, i.e. straight columns vs steeply sloping cones and connecting walls, is governed by the type and concentration of the oxidizing species, e.g. oxygen vs fluorine. Growth is believed to occur by a catalyst-free VLS (vapor-liquid-solid) mechanism that involves repetitive melting of the tips of the columns/cones and deposition there of the ablated flux of Si-containing vapor. Results are presented of a new investigation of how such different final microstructures as microcolumns or microcones joined by walls nucleate and develop. The changes in silicon surface morphology were systematically determined and compared as the number of pulsed KrF (248 nm) laser shots was increased from 25 to several thousand in both air and SF 6 . The experiments in air and SF 6 reveal significant differences in initial surface cracking and pattern formation. Consequently, local protrusions are first produced and column or cone/wall growth is initiated by different processes and at different rates. Differences in the spatial organization of column or cone/wall growth also are apparent

  18. Silica micro- and nanoparticles reduce the toxicity of surfactant solutions.

    Science.gov (United States)

    Ríos, Francisco; Fernández-Arteaga, Alejandro; Fernández-Serrano, Mercedes; Jurado, Encarnación; Lechuga, Manuela

    2018-04-20

    In this work, the toxicity of hydrophilic fumed silica micro- and nanoparticles of various sizes (7 nm, 12 nm, and 50 μm) was evaluated using the luminescent bacteria Vibrio fischeri. In addition, the toxicity of an anionic surfactant solution (ether carboxylic acid), a nonionic surfactant solution (alkyl polyglucoside), and a binary (1:1) mixture of these solutions all containing these silica particles was evaluated. Furthermore, this work discusses the adsorption of surfactants onto particle surfaces and evaluates the effects of silica particles on the surface tension and critical micellar concentration (CMC) of these anionic and nonionic surfactants. It was determined that silica particles can be considered as non-toxic and that silica particles reduce the toxicity of surfactant solutions. Nevertheless, the toxicity reduction depends on the ionic character of the surfactants. Differences can be explained by the different adsorption behavior of surfactants onto the particle surface, which is weaker for nonionic surfactants than for anionic surfactants. Regarding the effects on surface tension, it was found that silica particles increased the surface activity of anionic surfactants and considerably reduced their CMC, whereas in the case of nonionic surfactants, the effects were reversed. Copyright © 2018 Elsevier B.V. All rights reserved.

  19. Nano-TiCl4.SiO2: A Versatile and Efficient Catalyst for Synthesis of 14-aryl or alkyl-14H-dibenzo[a,j]xanthenes

    OpenAIRE

    B. F. Mirjalili; A. Bamoniri; L. Zamani

    2013-01-01

    Nano-silica supported titanium tetrachloride (TiCl4.SiO2) was prepared and used as an acid catalyst for the 14-aryl or alkyl-14H-dibenzo[a,,j]xanthenesreaction under solvent-free conditions. Compared to the classical 14-aryl or alkyl-14H-dibenzo[a,j]xanthenesreaction conditions, this method consistently has the advantage of excellent yields, mild reaction conditions, ease of workup, survival of different functional groups and short reaction times.

  20. Adsorption of dissymmetric cationic gemini surfactants at silica/water interface

    Science.gov (United States)

    Sun, Yuhai; Feng, Yujun; Dong, Hongwei; Chen, Zhi

    2007-05-01

    Adsorption of a series of cationic gemini surfactants 12-2- m ( m = 8, 12, 16) on the surface of silica was investigated. The critical micelle concentrations, cmcs, of cationic gemini surfactants in the initial solutions and in the supernatants were measured by conductometry and tensiometer. The changes in cmc values indicate that the ion exchanges take place between polar groups of gemini surfactants adsorbed and ions bound on the surface of silica. The adsorption isotherms of cationic gemini surfactants were obtained by a solution depletion method. Based on the driving force, the adsorption includes two steps, one of which is ion exchange, and the other is hydrophobic interaction. In each step, the tendency of surfactant molecules in the solution to form aggregates or to be adsorbed on the silica varies with their structures. The maximum adsorption amount of gemini surfactants on the silica, τmax, decreases as increasing in the length of one alkyl chain, m, from 8, 12 to 16. So the results show that the adsorption behaviors of gemini surfactants are closely related to the dissymmetry of gemini molecules.

  1. Thermal aromatic Claisen rearrangement and Strecker reaction of alkyl(allyl-aryl ethers under green reaction conditions: Efficient and clean preparation of ortho-allyl phenols (naphthols and alkyl(allyloxyarene-based γ-amino nitriles

    Directory of Open Access Journals (Sweden)

    Kheila N. Silgado-Gómez

    2017-11-01

    Full Text Available Chemical transformations of 13 diverse allyl(alkyl-aryl ethers, easily prepared using Williamson reaction of different hydroxyarenes and allyl bromide and alkyl (n-butyl, n-octyl bromides, were studied. Thermal aromatic Claisen rearrangement of allyl-aryl ethers to obtain ortho-allyl phenols (naphthols employing propylene carbonate as a nontoxic and biodegradable solvent was described for the first time. The use of this green solvent allowed to enhance notably product yields and reduce significantly the reaction time comparing with the use of 1,2-dichlorobenzene, toxic solvent, which is traditionally employed in this type of Claisen rearrangement. Three-component Strecker reaction of selected alkyl(allyl-aryl ethers with formyl function on aryl fragment and, piperidine and potassium cyanide in the presence of sulfuric acid supported on silica gel (SSA, SiO2-O-SO3H under mild reaction conditions was used in the preparation of new γ-amino nitriles, analogues of alkaloid girgensohnine [2-(4-hydroxyphenyl-2-(piperidin-1-ylacetonitrile], a perspective biological model in the search for new insecticidal agrochemicals against Aedes aegypti. The use of SSA, an inexpensive and reusable solid catalyst, allowed to obtain new series of 2-[4-alkyl(allyloxyphenyl]-2-(piperidin-1-ylacetonitriles in short time at room temperature with good yields.

  2. Chichibabin-type direct alkylation of pyridyl alcohols with alkyl lithium reagents.

    Science.gov (United States)

    Jeffrey, Jenna L; Sarpong, Richmond

    2012-11-02

    Direct C(6) alkylation of pyridyl alcohols can be achieved following an initial deprotonation of the hydroxy group. This transformation, which is believed to occur by a Chichibabin-type alkylation, avoids lateral deprotonation prior to pyridine ring alkylation and gives increased regioselectivity for C(6) over C(4) alkylation.

  3. Nano-TiCl4.SiO2: A Versatile and Efficient Catalyst for Synthesis of 14-aryl or alkyl-14H-dibenzo[a,j]xanthenes

    Directory of Open Access Journals (Sweden)

    B. F. Mirjalili

    2013-12-01

    Full Text Available Nano-silica supported titanium tetrachloride (TiCl4.SiO2 was prepared and used as an acid catalyst for the 14-aryl or alkyl-14H-dibenzo[a,,j]xanthenesreaction under solvent-free conditions. Compared to the classical 14-aryl or alkyl-14H-dibenzo[a,j]xanthenesreaction conditions, this method consistently has the advantage of excellent yields, mild reaction conditions, ease of workup, survival of different functional groups and short reaction times.

  4. Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

    KAUST Repository

    Maity, Niladri; Barman, Samir; Callens, Emmanuel; Samantaray, Manoja K.; Abou-Hamad, Edy; Minenkov, Yury; D'Elia, Valerio; Hoffman, Adam S.; Widdifield, Cory M.; Cavallo, Luigi; Gates, Bruce C.; Basset, Jean-Marie

    2015-01-01

    The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

  5. Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

    KAUST Repository

    Maity, Niladri

    2015-11-30

    The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

  6. Synthesis and evaluation of sequence-specific DNA alkylating agents: effect of alkylation subunits.

    Science.gov (United States)

    Shimizu, Tatsuhiko; Sasaki, Shunta; Minoshima, Masafumi; Shinohara, Ken-ichi; Bando, Toshikazu; Sugiyama, Hiroshi

    2006-01-01

    We have demonstrated that hairpin pyrrole (Py)- imidazole (Im) polyamide-CBI conjugates selectively alkylate predetermined sequences. In this study, we investigated the effect of alkylation subunits, for example conjugates 1-4 with three types of DNA alkylating units, and Py-Im polyamides with indole linker. Conjugate 3 and 4 selectively alkylated the predetermined sequences as described previously, while conjugates 1 and 2 alkylate at mismatched sites.

  7. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

    KAUST Repository

    Qureshi, Ziyauddin

    2017-01-05

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  8. SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

    KAUST Repository

    Qureshi, Ziyauddin; Hamieh, Ali Imad Ali; Barman, Samir; Maity, Niladri; Samantaray, Manoja; Ould-Chikh, Samy; Abou-Hamad, Edy; Falivene, Laura; D’ Elia, Valerio; Rothenberger, Alexander; Llorens, Isabelle; Hazemann, Jean-Louis; Basset, Jean-Marie

    2017-01-01

    Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

  9. Syntheses, characterization and adsorption properties for Pb{sup 2+} of silica-gel functionalized by dendrimer-like polyamidoamine and 5-sulfosalicylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Xiongzhi, E-mail: 2004046@glut.edu.cn; Luo, Liangliang; Chen, Ziyan; Liang, Kailing

    2016-02-28

    Graphical abstract: SEM images of APSG, PAMAM-1.0SSASG, PAMAM-2.0SSASG, PAMAM-3.0SSASG and PAMAM-4.0SSASG. - Highlights: • Silica-gel adsorbents PAMAM-n.0SSASG (n = 1–4) with dendrimer-like polyamidoamine and 5-sulfosalicylic acid as functional groups were prepared. • The generation increase of grafted PAMAM changed the pore diameter distribution of adsorbent and adsorption/desorption property of PAMAM-4.0SSASG for Pb{sup 2+} was the best of four adsorbents. • The priority of adsorption property of PAMAM-4.0SSASG was explained by steric hindrance effect of PAMAM on adsorption/desorption, and selective adsorption of 5-sulfosalicylic acid with Pb{sup 2+}. • Pb{sup 2+} in standard reference sample and sea water sample were preconcentrated with PAMAM-4.0SSASG as adsorbent and determined by GFAAS. - Abstract: Silica-gel adsorbents PAMAM-n.0SSASG (n = 1–4) with dendrimer-like polyamidoamine (PAMAM) and 5-sulfosalicylic acid as functional groups were prepared and characterized with FTIR, SEM, TG, elemental analysis and porous structure analysis. Micro-column enrichment and measurement of Pb{sup 2+} with graphite furnace atomic absorption spectroscopy (GFAAS) was studied with PAMAM-n.0SSASG (n = 1–4) as adsorbent. It was emphasized to investigate the relationship between dynamic adsorption/desorption rates, adsorption capacities, and grafting percentage of PAMAM onto silica-gel surface. Experiments showed that the generation increase of grafted PAMAM changed the pore diameter distribution of adsorbent and obviously improved adsorption/desorption property for Pb{sup 2+}. Adsorption capacity of PAMAM-n.0SSASG (n = 1–4) was 14.04, 17.43, 20.07 and 25.05 mg g{sup −1} for Pb{sup 2+} respectively. An enrichment factor of 200 was obtained with PAMAM-4.0SSASG as adsorbent and with 2000 mL Pb{sup 2+} solution (1.0 ng mL{sup −1}). The priority of adsorption property of PAMAM-4.0SSASG was explained by steric hindrance effect of PAMAM on adsorption/desorption, and

  10. Boronic acid functionalized silica microparticles for isolation of flavonoids from Hypericum perforatum

    Directory of Open Access Journals (Sweden)

    Onur Çetinkaya

    2017-10-01

    Full Text Available We have selectively separated cis- and/or vicinal-diol-containing flavonoids from Hypericum perfaratum (HP by adsorption/desorption using aminophenylboronic acid (APBA functionalized uniform (1.6 μm silica microparticles (BASPs synthesized via the Stöber method. Silica particles were alkylated by its terminal –OH with 3-aminopropyl trimethoxysilane (APTS, glutaraldehyde (GA and APBA. The results from model adsorption studies indicated that these microparticles selectively adsorbed quercetin and rutin but partially apigenin. The antioxidant and antiradical activities of the desorption solution were slightly higher than that of the post-adsorption solution. These results indicated that the BASP selectively adsorbed the cis- and/or vicinal antioxidant and antiradical flavonoids.

  11. [Alkylating agents].

    Science.gov (United States)

    Pourquier, Philippe

    2011-11-01

    With the approval of mechlorethamine by the FDA in 1949 for the treatment of hematologic malignancies, alkylating agents are the oldest class of anticancer agents. Even though their clinical use is far beyond the use of new targeted therapies, they still occupy a major place in specific indications and sometimes represent the unique option for the treatment of refractory diseases. Here, we are reviewing the major classes of alkylating agents and their mechanism of action, with a particular emphasis for the new generations of alkylating agents. As for most of the chemotherapeutic agents used in the clinic, these compounds are derived from natural sources. With a complex but original mechanism of action, they represent new interesting alternatives for the clinicians, especially for tumors that are resistant to conventional DNA damaging agents. We also briefly describe the different strategies that have been or are currently developed to potentiate the use of classical alkylating agents, especially the inhibition of pathways that are involved in the repair of DNA lesions induced by these agents. In this line, the development of PARP inhibitors is a striking example of the recent regain of interest towards the "old" alkylating agents.

  12. Synthesis of Novel Mesoporous Silica Materials with Hierarchical Pore Structures

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Suk Bon; Choi, Wang Kyu; Choi, Byung Seon; Moon, Jei Kwon [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2012-05-15

    Porous materials with various pore sizes in the range of micropore (< 2 nm), mesopore (2-50 nm), and macropore (> 50 nm) are attractive due to their many emerging applications such as catalysts, separation systems, and low dielectric constant materials. The discovery of new M41S mesoporous silica families with pore sizes larger than 2 nm in diameter in 1992 extended the applications into much wider pore ranges, bringing in a new prosperous era in porous material research. The synthesis of these silica materials has been mainly accomplished through a self-assembly between surfactant molecules and inorganic species under various pH conditions. Recently, core-shell nanoparticles with a silica core and mesoporous shell under basic conditions were synthesized using the silica nanoparticles as a core, and a silica precursor (TEOS) and cationic surfactant (CTABr) as a material for the formation of the mesoporous shell. The resultant materials were very monodispersive in size and showed a narrow pore size distribution in the range of ca 2-3 nm in diameter, depending on the alkyl-chain length of the surfactants used. In this work, the mesoporous shell coated-fumed silicas (denoted as MS M-5s) were synthesized by using fumed silica instead of the silica nanoparticle as a core based on previous reports. Also, the structural properties of the MS M-5s such as the specific surface area and pore volume were easily controlled by varying the amount of the silica precursor and surfactant. The resultant materials exhibited a BET surface area of ca 279-446 m{sup 2}/g and total pore volume of ca 0.64-0.74 cm{sup 3}/g and showed a narrow pore size distribution (PSD) due to the removal of the organic surfactant molecules

  13. Highly selective enrichment of phosphorylated peptides from peptide mixtures using titanium dioxide microcolumns

    DEFF Research Database (Denmark)

    Larsen, Martin Røssel; Thingholm, Tine E; Jensen, Ole N

    2005-01-01

    based on TiO2microcolumns and peptide loading in 2,5-dihydroxybenzoic acid (DHB). The effect of DHB was a very efficient reduction in the binding of nonphosphorylated peptides to TiO2 while retaining its high binding affinity for phosphorylated peptides. Thus, inclusion of DHB dramatically increased...... the selectivity of the enrichment of phosphorylated peptides by TiO2. We demonstrated that this new procedure was more selective for binding phosphorylated peptides than IMAC using MALDI mass spectrometry. In addition, we showed that LC-ESI-MSMS was biased toward monophosphorylated peptides, whereas MALDI MS...... was not. Other substituted aromatic carboxylic acids were also capable of specifically reducing binding of nonphosphorylated peptides, whereas phosphoric acid reduced binding of both phosphorylated and nonphosphorylated peptides. A putative mechanism for this intriguing effect is presented....

  14. The Scarlet Letter of Alkylation: A Mini Review of Selective Alkylating Agents

    OpenAIRE

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-01-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to “tame” the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it i...

  15. Mechanism of n-butane hydrogenolysis promoted by Ta-hydrides supported on silica

    KAUST Repository

    Pasha, Farhan Ahmad

    2014-06-06

    The mechanism of hydrogenolysis of alkanes, promoted by Ta-hydrides supported on silica via 2 ≡ Si-O- bonds, has been studied with a density functional theory (DFT) approach. Our study suggests that the initial monohydride (≡ Si-O-)2Ta(III)H is rapidly trapped by molecular hydrogen to form the more stable tris-hydride (≡ Si-O-) 2Ta(V)H3. Loading of n-butane to the Ta-center occurs through C-H activation concerted with elimination of molecular hydrogen (σ-bond metathesis). Once the Ta-alkyl species is formed, the C-C activation step corresponds to a β-alkyl transfer to the metal with elimination of an olefin. According to these calculations, an α-alkyl transfer to the metal to form a Ta-carbene species is of higher energy. The olefins formed during the C-C activation step can be rapidly hydrogenated by both mono- and tris-Ta-hydride species, making the overall process of alkane cracking thermodynamically favored. © 2014 American Chemical Society.

  16. Isobutane/olefin-alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Waitkamp, J.; Maixner, S.

    1983-11-01

    Isobutane/olefin-alkylation - technology and reaction mechanism of a refinery process for production of high octane gasoline components: The alkylation of i-butane with olefins, especially with butenes, is a process for the conversion of light byproducts of a catalytic cracker to high quality gasoline components. Alkylate is a complex mixture of i-paraffins containing 5 to ca. 12 carbon atoms. Due to their octane numbers the four trimethylpentane isomers are the most desirable product components. Indeed, under optimum process conditions these isomers are the main products. Presently, alkylation capacity in the western world amounts to more than 40x10/sup 6/ t/a. Most units are located in the USA. Two liquid-phase processes using sulfuric acid and hydrofluoric acid, respectively, are of commercial importance. At present, there is a definite trend towards HF-alkylation. The reaction mechanism which proceeds via carbocations, is extremely complex. It is composed of a great variety of individual steps. Modern mechanistic concepts are discussed.

  17. Determination of the sulfur mustard hydrolysis product thiodiglycol by microcolumn liquid chromatography coupled on-line with sulfur flame photometric detection using large-volume injections and peak

    NARCIS (Netherlands)

    Hooijschuur, E.W.J.; Kientz, C.E.; Brinkman, U.A.T.

    1999-01-01

    A selective, direct and relatively rapid method has been developed for the determination of thiodiglycol (TDG) in aqueous samples. TDG is the main hydrolysis product of the chemical warfare agent sulfur mustard. The method of analysis is based on the on-line coupling of reversed-phase microcolumn

  18. Development of silica RO membranes

    International Nuclear Information System (INIS)

    Ikeda, Ayumi; Kawamoto, Takashi; Matsuyama, Emi; Utsumi, Keisuke; Nomura, Mikihiro; Sugimoto, Masaki; Yoshikawa, Masato

    2012-01-01

    Silica based membranes have been developed by using a counter diffusion CVD method. Effects of alkyl groups in the silica precursors and deposition temperatures had investigated in order to control pore sizes of the silica membranes. In this study, this type of a silica membrane was applied for RO separation. Effects of silica sources, deposition temperatures and post treatments had been investigated. Tetramethoxysilane (TMOS), Ethyltrimethoxysilane (ETMOS) and Phenyltrimethoxysilane (PhTMOS) were used as silica precursors. A counter diffusion CVD method was carried out for 90 min at 270 - 600degC on γ-alumina capillary substrates (effective length: 50 mm, φ: 4 nm: NOK Co.). O 3 or O 2 was introduced into the inside of the substrate at the O 2 rate of 0.2 L min -1 . Ion beam irradiation was carried out for a post treatment using Os at 490 MeV for 1.0 x 10 10 ions cm -2 or 3.0 x 10 10 ions cm -2 . Single gas permeance was measured by using H 2 , N 2 and SF 6 . RO tests were employed at 3.0 or 5.4 MPa for 100 mg L -1 of feed NaCl solution. First, effects of the silica sources were investigated. The total fluxes increased by increasing N 2 permeance through the silica membrane deposited by ETMOS. The maximum NaCl rejection was 28.2% at 12.2 kg m -2 h -1 of the total flux through the membrane deposited at 270degC. N 2 permeance was 9.6 x 10 -9 mol m -2 s -1 Pa -1 . While, total fluxes through the membrane deposited by using PhTMOS were smaller than those through the ETMOS membranes. The phenyl groups for the PhTMOS membrane must be important for the hydrophobic properties through the membrane. Next, effects of ion beam irradiation were tested for the TMOS membranes. Water is difficult to permeate through the TMOS membranes due to the low N 2 permeance through the membrane (3.1 x 10 -11 mol m -2 s -1 Pa -1 ). N 2 permeance increased to 7.3 x 10 -9 mol m -2 s -1 Pa -1 by the irradiation. Irradiation amounts had little effects on N 2 permeance. However, NaCl rejections

  19. S-alkylation of soft scorpionates.

    Science.gov (United States)

    Rajasekharan-Nair, Rajeev; Moore, Dean; Chalmers, Kirsten; Wallace, Dawn; Diamond, Louise M; Darby, Lisa; Armstrong, David R; Reglinski, John; Spicer, Mark D

    2013-02-11

    The alkylation reactions of soft scorpionates are reported. The hydrotris(S-alkyl-methimazolyl)borate dications (alkyl = methyl, allyl, benzyl), which were prepared by the reaction of Tm(Me) anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C=S versus B-H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo-μ-aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ(3)-S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S-alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B-N bond in soft scorpionates, which has implications for their use in more advanced chemistry. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. The use of titanium dioxide micro-columns to selectively isolate phosphopeptides from proteolytic digests

    DEFF Research Database (Denmark)

    Thingholm, Tine E; Larsen, Martin R

    2009-01-01

    Titanium dioxide has very high affinity for phosphopeptides and it has become an efficient alternative to already existing methods for phosphopeptide enrichment from complex samples. Peptide loading in a highly acidic environment in the presence of 2,5-dihydroxybenzoic acid (DHB), phthalic acid......, or glycolic acid has been shown to improve selectivity significantly by reducing unspecific binding from nonphosphorylated peptides. The enriched phosphopeptides bound to the titanium dioxide are subsequently eluted from the micro-column using an alkaline buffer. Titanium dioxide chromatography is extremely...... tolerant towards most buffers used in biological experiments. It is highly robust and as such it has become one of the methods of choice in large-scale phospho-proteomics. Here we describe the protocol for phosphopeptide enrichment using titanium dioxide chromatography followed by desalting...

  1. On-line dynamic fractionation and automatic determination of inorganic phosphorous in environmental solid substrates exploiting sequential injection microcolumn extraction and flow injection analysi

    DEFF Research Database (Denmark)

    Buanuam, Janya; Miró, Manuel; Hansen, Elo Harald

    2006-01-01

    Sequential injection microcolumn extraction (SI-MCE) based on the implementation of a soil containing microcartridge as external reactor in a sequential injection network is, for the first time, proposed for dynamic fractionation of macronutrients in environmental solids, as exemplified by the pa......Sequential injection microcolumn extraction (SI-MCE) based on the implementation of a soil containing microcartridge as external reactor in a sequential injection network is, for the first time, proposed for dynamic fractionation of macronutrients in environmental solids, as exemplified...... by the partitioning of inorganic phosphorous in agricultural soils. The on-line fractionation method capitalises on the accurate metering and sequential exposure of the various extractants to the solid sample by application of programmable flow as precisely coordinated by a syringe pump. Three different soil phase...... associations for phosphorus, that is, exchangeable, Al- and Fe-bound and Ca-bound fractions, were elucidated by accommodation in the flow manifold of the 3 steps of the Hietjles-Litjkema (HL) scheme involving the use of 1.0 M NH4Cl, 0.1 M NaOH and 0.5 M HCl, respectively, as sequential leaching reagents...

  2. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    Energy Technology Data Exchange (ETDEWEB)

    Albright, L.F. [Purdue Univ., West Lafayette, IN (United States); Kranz, K.E.; Masters, K.R. [STRATCO, Inc., Leawood, KS (United States)

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  3. N-Alkylation Using Sodium Triacetoxyborohydride with Carboxylic Acids as Alkyl Sources.

    Science.gov (United States)

    Tamura, Satoru; Sato, Keigo; Kawano, Tomikazu

    2018-01-01

    A versatile N-alkylation was performed using sodium triacetoxyborohydride and carboxylic acid as an alkyl source. The combination of these reagents furnished products different from those given previously by a similar reaction. Moreover, the mild conditions of our method allowed some functional groups to remain through the reaction, whereas they would react and be converted into other moieties in the similar reductive N-alkylation reported previously. Herein, we provide a new procedure for the preparation of various compounds containing nitrogen atoms.

  4. Fast-turnaround alkyl nitrate measurements during the PROPHET 1998 summer intensive

    Science.gov (United States)

    Ostling, Kristi; Kelly, Brendan; Bird, Stephen; Bertman, Steven; Pippin, Margaret; Thornberry, Troy; Carroll, Mary Anne

    2001-10-01

    An automated gas chromatographic system for making fast-turnaround measurements of alkyl nitrates was developed and tested. Every 30 min, samples were automatically acquired on a 1/16-inch OD Tenax trap made from fused silica-lined stainless steel tubing and injected by thermal desorption into the gas chromatograph. The system exhibited good chromatographic resolution, minimal breakthrough, and on-trap stability for C3-C5 nitrates. The detection limit of the instrument was Biological Station in northern Michigan during the summer of 1998 from July 15 to August 22. Ambient results show a significant dynamic range with absolute levels affected by air mass history and pollution sources. The sum of measured C3-C5 alkyl nitrates obtained during this intensive ranged from 3.45 to 65.8 pptv, with a mean of 18.6 pptv and contributed 1% on average to total NOy, with a range of 0.5% to 3%. Differences in the contribution to NOy are found when the data are filtered according to air mass origin. A positive relationship between n-propyl nitrate and peroxypropionyl nitrate was observed over the course of the intensive.

  5. The Scarlet Letter of Alkylation: A Mini Review of Selective Alkylating Agents

    Science.gov (United States)

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-01-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to “tame” the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it is referred to herein, constitutes an extremely nascent and dynamic field in oncology. The pharmacodynamic response to this selective strategy depends on a delicate kinetic balance between specificity and the rate and extent of binding. Three representative compounds are presented: RRx-001, 3-bromopyruvate, and TH-302. The main impetus for the development of these compounds has been the avoidance of the serious complications of traditional alkylating agents; therefore, it is the thesis of this review that they should not experience stigma by association. PMID:22937173

  6. The scarlet letter of alkylation: a mini review of selective alkylating agents.

    Science.gov (United States)

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-08-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to "tame" the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it is referred to herein, constitutes an extremely nascent and dynamic field in oncology. The pharmacodynamic response to this selective strategy depends on a delicate kinetic balance between specificity and the rate and extent of binding. Three representative compounds are presented: RRx-001, 3-bromopyruvate, and TH-302. The main impetus for the development of these compounds has been the avoidance of the serious complications of traditional alkylating agents; therefore, it is the thesis of this review that they should not experience stigma by association.

  7. Alkyl and aryl phosphorodiiodidites. Pt. 2

    International Nuclear Information System (INIS)

    Feshchenko, N.G.; Kostina, V.G.

    1976-01-01

    Alkyl phosphorodiiodidites are formed in the reactions of alkyl phosphorodichloridites with lithium iodide. They are stable at -60 to -50 0 . When warmed to 20 0 , they disproportionate with conversion into trialkyl phosphites and phosphorus triiodide. The latter also react together and give alkyl iodides, diphosphorus tetraiodide, and a polymer of unestablished structure. Diaryl and dialkyl phosphoriodidites are stable only in solution at low temperatures. They disproportionate in a similar way to aryl and alkyl phosphorodiiodidites. Alkyl phosphorodiiodidites react with iodine with the formation of alkyl iodides and phosphoryl iodide

  8. Photoinduced alkylation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dondi, D.; Fagnoni, M.; Albini, A.

    2002-07-01

    Some {alpha}{beta}-unsaturated aldehydes have been alkylated generating alkyl radicals from alcohols and dioxolanes in mixed aqueous-organic solution though photoinduced hydrogen abstraction by disodium benzophenondisulfonate when exposed to solar light (6 to 14 hours for 10 g amounts). (Author) 8 refs.

  9. DNA-directed alkylating ligands as potential antitumor agents: sequence specificity of alkylation by intercalating aniline mustards.

    Science.gov (United States)

    Prakash, A S; Denny, W A; Gourdie, T A; Valu, K K; Woodgate, P D; Wakelin, L P

    1990-10-23

    The sequence preferences for alkylation of a series of novel parasubstituted aniline mustards linked to the DNA-intercalating chromophore 9-aminoacridine by an alkyl chain of variable length were studied by using procedures analogous to Maxam-Gilbert reactions. The compounds alkylate DNA at both guanine and adenine sites. For mustards linked to the acridine by a short alkyl chain through a para O- or S-link group, 5'-GT sequences are the most preferred sites at which N7-guanine alkylation occurs. For analogues with longer chain lengths, the preference of 5'-GT sequences diminishes in favor of N7-adenine alkylation at the complementary 5'-AC sequence. Magnesium ions are shown to selectively inhibit alkylation at the N7 of adenine (in the major groove) by these compounds but not the alkylation at the N3 of adenine (in the minor groove) by the antitumor antibiotic CC-1065. Effects of chromophore variation were also studied by using aniline mustards linked to quinazoline and sterically hindered tert-butyl-9-aminoacridine chromophores. The results demonstrate that in this series of DNA-directed mustards the noncovalent interactions of the carrier chromophores with DNA significantly modify the sequence selectivity of alkylation by the mustard. Relationships between the DNA alkylation patterns of these compounds and their biological activities are discussed.

  10. Williamson alkylation approach to the synthesis of poly(alkyl vinyl ether) copolymers

    International Nuclear Information System (INIS)

    Markova, D.; Christova, D.; Velichkova, R.

    2008-01-01

    A method for synthesis of poly(alkyl vinyl ether-co-vinyl alcohol) copolymers was developed based on the Williamson's alkylation of poly(vinyl acetate) (PVAc) with alkyl iodides. The influence of the alkylating agent and the reaction conditions on the efficiency of the modification reaction was investigated. The copolymers obtained were characterized by means of 1 H NMR and GPC. It was proved that by applying the proposed method copolymers of different composition and properties containing methyl vinyl ether, ethyl vinyl ether as well as n-butyl vinyl ether units could be prepared. Poly(methyl vinyl ether-co-vinyl alcohol)s of high degree of methylation exhibit sharp temperature response at 38-39 deg C in aqueous solution typical of the so-called smart polymers. (authors)

  11. Poly(alkyl acrylate) nonparticles

    International Nuclear Information System (INIS)

    Kreuter, J.

    1985-01-01

    This study deals with the preparation of poly(alkyl acrylic) and poly(alkyl cyanocrylic) nanoparticles. Nonoparticles are solid colloidal particles, consisting of macromolecular materials in which drugs or biologically active materials are dissolved, entrapped, and encapsulated, and/or to which the active substance is adsorbed or attached. Poly(alkyl acrylic) nanoparticles are much more slowly biodegradable than poly(alkyl cyanoacrylate) nanoparticles, and are thus more suitable for drug delivery purposes. Poly(methyl methacrylate) is the material of choice for the use of nanoparticles as an adjuvant for vaccines and are produced by emulsifier-free polymerization in aqueous media. The polymerization, which can be initiated with gamma rays or with potassium peroxodisulfate, is described

  12. Structure and thermal performance of poly(ethylene glycol) alkyl ether (Brij)/porous silica (MCM-41) composites as shape-stabilized phase change materials

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lingjian; Shi, Haifeng, E-mail: haifeng.shi@gmail.com; Li, Weiwei; Han, Xu; Zhang, Xingxiang, E-mail: zhangpolyu@gmail.com

    2013-10-20

    Graphical abstract: The maximum 50 wt% Brij58 is loaded into the porous MCM-41 networks, and a new peak at 18.8° in XRD patterns confirmed the changes of crystallization behavior of Brij58 against the bulk one. - Highlights: • Poly(ethylene glycol) hexadecyl ether and poly(ethylene glycol) octadecyl ether have the good thermal storage ability. • New peak at 18.8° proved the coexisted confined crystallization and nucleation-induced crystallization. • Poly(ethylene glycol) alkyl ether/MCM-41 PCMs exhibits the good thermal stability. - Abstract: A series of shape-stabilized phase change materials (PCMs), composed of poly(ethylene glycol) hexadecyl ether (Brij58) or poly(ethylene glycol) octadecyl ether (Brij76) and porous silica (MCM-41), were prepared by the physical mixing method. The structure, thermal stability, energy storage ability and crystallization behavior of these composites are deeply investigated and characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and thermogravimetric analysis (TGA). Obvious phase transition behavior and energy storage capability are observed for these Brij/MCM-41 composites, and the heat storage efficiency increased with the weight of Brij component. New peak at 18.8° demonstrated that the pore size and the surface adsorption ability of MCM-41 affect the crystallization behavior of Brij molecule. The crystalline structure and energy storage ability of these Brij/MCM-41 composites are discussed based on the crystallization process.

  13. Embryotoxicity induced by alkylating agents. Some methodological aspects of DNA alkylation studies in murine embryos using ethylmethanesulfonate.

    Science.gov (United States)

    Platzek, T; Bochert, G; Rahm, U; Neubert, D

    1987-05-01

    Synthesis and spectroscopic analysis of some alkylated DNA purine bases are described. HPLC separation methods are developed for the determination of DNA alkylation rates in mammalian embryonic tissues. Following treatment of pregnant mice with the ethylating agent ethylmethanesulfonate (EMS), an appreciable amount of alkylation (ethylation and methylation) was found in the nuclear DNA of the embryos during organogenesis. The results are discussed in context of our thesis that a certain amount of DNA alkylation in the embryos is correlated to the teratogenic potential of alkylating agents.

  14. Thioimidazolium Ionic Liquids as Tunable Alkylating Agents.

    Science.gov (United States)

    Guterman, Ryan; Miao, Han; Antonietti, Markus

    2018-01-19

    Alkylating ionic liquids based on the thioimidazolium structure combine the conventional properties of ionic liquids, including low melting point and nonvolatility, with the alkylating function. Alkyl transfer occurs exclusively from the S-alkyl position, thus allowing for easy derivatization of the structure without compromising specificity. We apply this feature to tune the electrophilicty of the cation to profoundly affect the reactivity of these alkylating ionic liquids, with a caffeine-derived compound possessing the highest reactivity. Anion choice was found to affect reaction rates, with iodide anions assisting in the alkylation reaction through a "shuttling" process. The ability to tune the properties of the alkylating agent using the toolbox of ionic liquid chemistry highlights the modular nature of these compounds as a platform for alkylating agent design and integration in to future systems.

  15. Outlook for the U.S. alkylation industry

    International Nuclear Information System (INIS)

    Felten, J.R.; Bradshaw, T.; McCarthy, K.

    1994-01-01

    Alkylation has long been recognized in the refining industry as one of the best options to convert refinery olefins into valuable, clean, high octane blending components. In fact, refinery alkylation is a preferred source of blending stocks for reformulated gasoline. However, the hydrofluoric acid (HF) alkylation process and, to a lesser extent, the sulfuric acid (SA) process have come under increasing pressure in the US due to safety and environmental concerns. This paper examines the current outlook for the US alkylation industry including: key trends and driving forces in the industry, the impact of environmental issues on both HF and SA alkylation, US alkylation supply/demand forecast including the outlook for oxygenates, how US refines will respond to the increased demand and restricted supply for alkylates, and the outlook for new solid acid alkylation (SAC) technology

  16. Microcolumn high pressure liquid chromatography with a glass-frit nebulizer interface for plasma emission detection

    International Nuclear Information System (INIS)

    Ibrahim, M.; Nisamaneepong, W.; Caruso, J.

    1985-01-01

    Microcolumn high pressure liquid chromatography (micro-HPLC) is rapidly gaining recognition as a practical separation tool for organometallic compounds. The use of the inductively coupled plasma (ICP) as a detector for micro-HPLC is studied. Several miniaturized glass-frit nebulizers are investigated as interfaces between the output of the microbore column and the ICP torch. Their performance with aqueous and methanolic solutions is evaluated by direct nebulization and flow injection analysis. The most efficient of these nebulizers is used in the micro-HPLC/ICP study of some Cd, Pb, and Zn organometallic compounds. Detection limits of 1.92 ng of Pb for tetramethyllead and 5.01 ng of Pb for tetraethyllead are obtained and compared with regular HPLC/ICP of these same compounds. Approximately equivalent detection limits were obtained when using a microwave induced plasma as an alternate plasma source

  17. Graft copolymerization of a series of alkyl acrylates and alkyl methacrylates onto polyethylene

    International Nuclear Information System (INIS)

    Zurakowska-Orszagh, J.; Soerjosoeharto, K.; Busz, W.; Oldziejewski, J.

    1977-01-01

    Graft copolymerization of a series of alkyl acrylates and alkyl methacrylates into polyethylene of Polish production was investigated, using benzoyl peroxide as the initiator as well as preirradiation technique, namely ionizing radiation from a 60 Co γ-source. The effect of α-carbon methyl substituent of methacrylates as well as the influence of the length of alkyl chains in the ester groups of both series of monomers into the grafting process was observed. The ungrafted and some of the grafted polyethylene film obtained was studied by infrared spectrophotometry. (author)

  18. Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

    Science.gov (United States)

    Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

    2014-02-05

    The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

  19. Interfce alkylation of ethyldiphenylphosphinylacetate

    International Nuclear Information System (INIS)

    Yarkevich, A.N.; Tsvetkov, E.N.

    1994-01-01

    The paper deals with the alkylation of the methyline group of ethyldiphenylphosphinylacetate (1) by different alkylating agents in the presence of Cs 2 CO 3 . In all cases the application of Cs 2 CO 3 results in a significant increase of reaction rate. 10 refs., 3 tabs

  20. Formation of enamines by alkylation of imines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1966-01-01

    cf. CA 64, 12473c. With ice-cooling, 1 equiv. alkylating agent was added to one equiv. of the imine in 1M soln. in a solvent in the presence of NaH to give both N- and C-alkylated products. The following summarizes the date (imine, solvent, alkylating agent, % unreacted imine, % N-alkylated product,

  1. Sulfonium Salts as Alkylating Agents for Palladium-Catalyzed Direct Ortho Alkylation of Anilides and Aromatic Ureas.

    Science.gov (United States)

    Simkó, Dániel Cs; Elekes, Péter; Pázmándi, Vivien; Novák, Zoltán

    2018-02-02

    A novel method for the ortho alkylation of acetanilide and aromatic urea derivatives via C-H activation was developed. Alkyl dibenzothiophenium salts are considered to be new reagents for the palladium-catalyzed C-H activation reaction, which enables the transfer of methyl and other alkyl groups from the sulfonium salt to the aniline derivatives under mild catalytic conditions.

  2. Molecular design of sequence specific DNA alkylating agents.

    Science.gov (United States)

    Minoshima, Masafumi; Bando, Toshikazu; Shinohara, Ken-ichi; Sugiyama, Hiroshi

    2009-01-01

    Sequence-specific DNA alkylating agents have great interest for novel approach to cancer chemotherapy. We designed the conjugates between pyrrole (Py)-imidazole (Im) polyamides and DNA alkylating chlorambucil moiety possessing at different positions. The sequence-specific DNA alkylation by conjugates was investigated by using high-resolution denaturing polyacrylamide gel electrophoresis (PAGE). The results showed that polyamide chlorambucil conjugates alkylate DNA at flanking adenines in recognition sequences of Py-Im polyamides, however, the reactivities and alkylation sites were influenced by the positions of conjugation. In addition, we synthesized conjugate between Py-Im polyamide and another alkylating agent, 1-(chloromethyl)-5-hydroxy-1,2-dihydro-3H-benz[e]indole (seco-CBI). DNA alkylation reactivies by both alkylating polyamides were almost comparable. In contrast, cytotoxicities against cell lines differed greatly. These comparative studies would promote development of appropriate sequence-specific DNA alkylating polyamides against specific cancer cells.

  3. Bis(trialkylsilyl) peroxides as alkylating agents in the copper-catalyzed selective mono-N-alkylation of primary amides.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-06-13

    The copper-catalyzed selective mono-N-alkylation of primary amides with bis(trialkylsilyl) peroxides as alkylating agents was reported. The results of a mechanistic study suggest that this reaction should proceed via a free radical process that includes the generation of alkyl radicals from bis(trialkylsilyl) peroxides.

  4. 40 CFR 721.9892 - Alkylated urea.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under this...

  5. Identify alkylation hazards

    International Nuclear Information System (INIS)

    Scott, B.

    1992-01-01

    This paper reports that extensive experience shows that alkylation plants regardless of acid catalyst choice, can be operated safely, and with minimum process risk to employees or neighbors. Both types of plants require a comprehensive and fully supported hazard management program that accounts for differing physical properties of the acids involved. Control and mitigation cost to refiners will vary considerably from plant to plant and location to location. In the author's experience, the order of magnitude costs will be about $1 to $2 million for a sulfuric acid (SA) alkylation plant, and about $10 to $15 million for a hydrofluoric acid (HF) plant. These costs include water supply systems and impoundment facilities for contaminated runoff water. The alkylation process, which chemically reacts isobutane and light olefins in the presence of a strong acid catalyst into a premium gasoline component is described

  6. Determination of reaction rate constants for alkylation of 4-(p-nitrobenzyl) pyridine by different alkylating agents.

    Science.gov (United States)

    Walles, S A

    1980-02-01

    The rate constants have been determined for the reaction between some different alkylating agents and 4-(p-nitrobenzyl) pyridine (NBP) in methanol. These constants have been compared with those for alkylation of aniline in water. All the constants were lower in methanol than in water but in different degrees. The rate constants of the different alkylating agents have been calculated at a nucleophilic strength n=2. The genetic risk defined as the degree of alkylation of a nucleophile (n=2) is equivalent to the rate constant kn=2 and the target dose. The dependence of the genetic risk on the rate constant (kn=2) is discussed.

  7. Alkylation of enolate anions formation of enol ethers

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The alkylation of ambident enolate anions-obtained from aliphatic ketones (and one particular type of aldehyde)-was studied using various solvents, bases, alkylating agents and substrates. Alkylation with a reactive alkylating agent (dialkyl sulfates, triethyloxonium fluoroborate) in an aprotic

  8. DNA minor groove targeted alkylating agents based on bisbenzimidazole carriers: synthesis, cytotoxicity and sequence-specificity of DNA alkylation.

    Science.gov (United States)

    Smaill, J B; Fan, J Y; Denny, W A

    1998-12-01

    A series of bisbenzimidazoles bearing a variety of alkylating agents [ortho- and meta-mustards, imidazolebis(hydroxymethyl), imidazolebis(methylcarbamate) and pyrrolebis(hydroxymethyl)], appended by a propyl linker chain, were prepared and investigated for sequence-specificity of DNA alkylation and their cytotoxicity. Previous work has shown that, for para-aniline mustards, a propyl linker is optimal for cytotoxicity. Alkaline cleavage assays using a variety of different labelled oligonucleotides showed that the preferred sequences for adenine alkylation were 5'-TTTANANAANN and 5'-ATTANANAANN (underlined bases show the drug alkylation sites), with AT-rich sequences required on both the 5' and 3' sides of the alkylated adenine. The different aniline mustards showed little variation in alkylation pattern and similar efficiencies of DNA cross-link formation despite the changes in orientation and positioning of the mustard, suggesting that the propyl linker has some flexibility. The imidazole- and pyrrolebis(hydroxymethyl) alkylators showed no DNA strand cleavage following base treatment, indicating that no guanine or adenine N3 or N7 adducts were formed. Using the PCR-based polymerase stop assay, these alkylators showed PCR blocks at 5'-C*G sites (the * nucleotide indicates the blocked site), particularly at 5'-TAC*GA 5'-AGC*GGA, and 5'-AGCC*GGT sequences, caused by guanine 2-NH2 lesions on the opposite strand. Only the (more reactive) imidazolebis(methylcarbamoyl) and pyrrolebis(hydroxymethyl) alkylators demonstrated interstrand cross-linking ability. All of the bifunctional mustards showed large (approximately 100-fold) increases in cytotoxicity over chlorambucil, with the corresponding monofunctional mustards being 20- to 60-fold less cytotoxic. These results suggest that in the mustards the propyl linker provides sufficient flexibility to achieve delivery of the alkylator to favoured (adenine N3) sites in the minor groove, regardless of its exact geometry with

  9. The application of micro-column solid phase extraction techniques for the determination of rare earth elements in actinide containing matrices

    International Nuclear Information System (INIS)

    Carney, K.P.; Cummings, D.G.

    1995-01-01

    The design and characterization of an argon segmented-solid phase extraction system is described. A 200 ul volume micro-column has been constructed for the preconcentration of rare earth elements (REEs) from salt matrices containing uranium. An inductively coupled plasma atomic emission spectrometer has been utilized for simultaneous detection of Sr, Y and the REEs (namely Ce, Eu, La, Nd, Pr, Sm) at levels ranging from 5- to 2000 ppm in LiCl/KCl samples containing U. Preconcentration factors of 100 fold have been demonstrated. The precision, linear dynamic range and column performance of the system will be presented. (author). 5 refs., 5 figs., 3 tabs

  10. Alkylation of reticular polymers of ethynyl piperidol by alkyl halogen and investigation of the swelling of the products in water

    International Nuclear Information System (INIS)

    Khakimkhodjaev, S.N.; Khalikov, D.Kh.

    1999-01-01

    In the paper the results of investigation on alkylation of reticular polymer of ethyl piperidol by methyl Iodide and ethyl Iodide are adduced. It have been shown that in the first case the reaction of an alkylation proceeds up to 100% of a degree of completion. In the second case of an alkylation the highest degree of alkylation reaches only 60% which is connected with formation of secondary structures. In both cases the process of an alkylation results in deriving highly swelled system

  11. The alkylation of imine anions formation of enamines

    NARCIS (Netherlands)

    Heiszwolf, G.J.; Kloosterziel, H.

    1970-01-01

    The ambident anions derived from imines were alkylated using a variety of solvents and alkylating agents. Under reactive conditions enamines (N-alkylation) are formed as the main products instead of the usually obsd. homologous imines (C-alkylation). The influence of the type of imine, solvent, and

  12. Quantitative estimation of the extent of alkylation of DNA following treatment of mammalian cells with non-radioactive alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Snyder, R.D. (Univ. of Tennessee, Oak Ridge); Regan, J.D.

    1981-01-01

    Alkaline sucrose sedimentation has been used to quantitate phosphotriester formation following treatment of human cells with the monofunctional alkylating agents methyl and ethyl methanesulfonate. These persistent alkaline-labile lesions are not repaired during short-term culture conditions and thus serve as a useful and precise index of the total alkylation of the DNA.Estimates of alkylation by this procedure compare favorably with direct estimates by use of labeled alkylating agents.

  13. Thermogravimetric studies on alkyl methacrylate polymers and poly(alkyl methacrylate)-grafted polypropylene fibers

    International Nuclear Information System (INIS)

    Hayakawa, Kiyoshi; Taoda, Hiroshi; Kawase, Kaoru; Tazawa, Masato; Yamakita, Hiromi

    1986-01-01

    Thermal behavior of several kinds of poly (alkyl methacrylate) and polypropylene-g-poly (alkyl methacrylate) fibers prepared by γ-irradiation was investigated by thermogravimetric measurements with the intermittent analysis of the gaseous products. The degradation of poly (methyl methacrylate) proceeded according to the deploymerization mechanism reproducing the pristine monomer exclusively. The thermogram in inert atmosphere showed the features of a two-step depolymerization, while in air it showed no such a stepwise decrease with the elevating temperature. The dissolution-precipitation treatment of polymer seemed to affect the decomposition behavior. On other alkyl methacrylate polymers, the thermal decomposition generally proceeded also according to the depolymerization mechanism. But, for instance, at least two kinds of products besides its own monomer were formed from poly (isobutyl methacrylate), and their relative fractions differed with the temperature. Polypropylene-g-poly (alkyl methacrylate) fibers showed lowering of initiation temperature of decomposition with the increase in extent of the grafting, and their initiation temperatures of decomposition in air were lower than those in inert atmosphere. (author)

  14. Influence of the ammonium hydroxide concentration in morphological control of meso porous silica particles

    International Nuclear Information System (INIS)

    Yoon, Sukbon; Jung, Chonghun; Yoon, Inho; Kim, Changki; Choi, Wangkyu; Moon, Jeikwon

    2012-01-01

    The discovery of new M41S meso porous silica families in 1992 extended the applications into much wider pore ranges, bringing in a new prosperous era in porous material research. The synthesis of these meso porous silicas has been mainly accomplished through a self-assembly between surfactant molecules and inorganic species under various pH conditions. Meanwhile, many studies have been conducted on the application as catalysts, adsorbents, and packing materials for separation columns due to their unique properties such as high specific surface area, large pore volume, tuneable pore size, and narrow pore size distribution. The pore sizes of these materials can be easily controlled by changing the alkyl-chain length of the surfactant used. However, the control of the morphology and the pore structure is not so common. The morphological control of these materials in particular is one of the major challenges for their industrial application. Recently, the meso porous silica materials with various shapes such as fibers, films, polyhedral particles, and spheres have been reported. In our previous study, the core-shell nanoparticles with a silica core and a meso porous shell under basic conditions were synthesized using the silica nanoparticles as a core and tetraethyl orthosilicate (TEOS)-cetyltrimethylammonium bromide (CTABr)-NH 4 OH-H 2 O-C 2 H 5 OH system. In this work, we report the synthesis of the most well known hexagonal MCM-41 among three main mesophases in the M41S families using TEOS-CTABr-NH 4 OH-H 2 O system. Also, in the control of the morphology and pore structure of the meso porous silica materials, the influence of the NH 4 OH concentration was investigated

  15. Manganese-catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-N-Heteroaromatics by Alcohols.

    Science.gov (United States)

    Kempe, Rhett; Zhang, Guoying; Irrgang, Torsten; Dietel, Thomas; Kallmeier, Fabian

    2018-05-02

    Catalysis involving earth-abundant transition metals is an option to help save our rare noble metal resources and is especially interesting if novel reactivity or selectivity patterns are observed. We report here on a novel reaction: the dehydrogenative alkylation or α-olefination of alkyl-N-heteroaromatics by alcohols. Manganese complexes developed in our laboratory catalyze the reaction efficiently. Fe and Co complexes stabilized by such ligands are essentially inactive. Hydrogen is liberated during the reaction and bromo or iodo functional groups and olefins can be tolerated. A variety of alkyl-N-heteroaromatics can be functionalized, and benzyl and aliphatic alcohols undergo the reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. DNA modification by alkylating compounds

    Energy Technology Data Exchange (ETDEWEB)

    Kruglyakova, E.E.

    1985-09-01

    Results are given for research on the physico-chemical properties of alkylating compounds - nitroso alkyl ureas (NAU) which possess a broad spectrum of biological activity, such as mutagenic, carcinogenic, and anti-tumor action that is due to the alkylation and carbamoylation of DNA as well as other cellular components. Identified chemical products of NAU interaction with DNA and its components are cited. Structural conversions of a DNA macromolecule resulting from its chemical modification are examined. NAU are used to discuss possible biological consequences of DNA modification. 148 references.

  17. Selective extraction of phospholipids from dairy products by micro-solid phase extraction based on titanium dioxide microcolumns followed by MALDI-TOF-MS analysis

    DEFF Research Database (Denmark)

    Calvano, Cosima; Jensen, Ole; Zambonin, Carlo

    2009-01-01

    A new micro-solid phase extraction (micro-SPE) procedure based on titanium dioxide microcolumns was developed for the selective extraction of phospholipids (PLs) from dairy products before matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis. All...... the extraction steps (loading, washing, and elution) have been optimized using a synthetic mixture of PLs standard and the procedure was subsequently applied to food samples such as milk, chocolate milk and butter. The whole method demonstrated to be simpler than traditional approaches and it appears very...

  18. Mechanisms of action of quinone-containing alkylating agents: DNA alkylation by aziridinylquinones.

    Science.gov (United States)

    Hargreaves, R H; Hartley, J A; Butler, J

    2000-11-01

    Aziridinyl quinones can be activated by cellular reductases eg. DT-diaphorase and cytochrome P450 reductase to form highly reactive DNA alkylating agents. The mechanisms by which this activation and alkylation take place are many and varied. Using clinically relevant and experimental agents this review will describe many of these mechanisms. The agents discussed are Mitomycin C, EO9 and analogues, diaziridinylbenzoquinones and the pyrrolo[1, 2-alpha]benzimidazolequinones.

  19. Distribution of methyl and ethyl adducts following alkylation with monofunctional alkylating agents.

    Science.gov (United States)

    Beranek, D T

    1990-07-01

    Alkylating agents, because of their ability to react directly with DNA either in vitro or in vivo, or following metabolic activation as in the case of the dialkylnitrosamines, have been used extensively in studying the mechanisms of mutagenicity and carcinogenicity. Their occurrence is widespread in the environment and human exposure from natural and pollutant sources is universal. Since most of these chemicals show varying degrees of both carcinogenicity and mutagenicity, and exhibit compound-specific binding patterns, they provide an excellent model for studying molecular dosimetry. Molecular dosimetry defines dose as the number of adducts bound per macromolecule and relates the binding of these adducts to the human mutagenic or carcinogenic response. This review complies DNA alkylation data for both methylating and ethylating agents in a variety of systems and discusses the role these alkylation products plays in molecular mutagenesis.

  20. Effect of aluminum alkyls on a homogeneous and silica-supported phenoxy-imine titanium catalyst for ethylene trimerization

    NARCIS (Netherlands)

    Karbach, Fabian F.; Severn, John R.; Duchateau, Robbert

    A phenoxy-imine titanium catalyst (FI-catalyst) for selective ethylene trimerization was immobilized on methyl aluminoxane (MAO) pretreated silica and its activity and selectivity was compared with that of the corresponding homogeneous catalyst system. The homogeneous and heterogeneous ethylene

  1. Cytotoxicity of alkylating agents towards sensitive and resistant strains of Escherichia coli in relation to extent and mode of alkylation of cellular macromolecules and repair of alkylation lesions in deoxyribonucleic acids.

    Science.gov (United States)

    Lawley, P D; Brookes, P

    1968-09-01

    1. A quantitative study was made of the relationship between survival of colony-forming ability in Escherichia coli strains B/r and B(s-1) and the extents of alkylation of cellular DNA, RNA and protein after treatment with mono- or di-functional sulphur mustards, methyl methanesulphonate or iodoacetamide. 2. The mustards and methyl methanesulphonate react with nucleic acids in the cells, in the same way as found previously from chemical studies in vitro, and with proteins. Iodoacetamide reacts only with protein, principally with the thiol groups of cysteine residues. 3. The extents of alkylation of cellular constituents required to prevent cell division vary widely according to the strain of bacteria and the nature of the alkylating agent. 4. The extents of alkylation of the sensitive and resistant strains at a given dose of alkylating agent do not differ significantly. 5. Removal of alkyl groups from DNA of cells of the resistant strains B/r and 15T(-) after alkylation with difunctional sulphur mustard was demonstrated; the product di(guanin-7-ylethyl) sulphide, characteristic of di- as opposed to mono-functional alkylation, was selectively removed; the time-scale of this effect suggests an enzymic rather than a chemical mechanism. 6. The sensitive strain B(s-1) removed alkyl groups from DNA in this way only at very low extents of alkylation. When sensitized to mustard action by treatment with iodoacetamide, acriflavine or caffeine, the extent of alkylation of cellular DNA corresponding to a mean lethal dose was decreased to approximately 3 molecules of di(guanin-7-ylethyl) sulphide in the genome of this strain. 7. Relatively large numbers of monofunctional alkylations per genome can be withstood by this sensitive strain. Iodoacetamide had the weakest cytotoxic action of the agents investigated; methyl methanesulphonate was significantly weaker in effect than the monofunctional sulphur mustard, which was in turn weaker than the difunctional sulphur mustard. 8

  2. Single Site Silica Supported Tetramethyl Niobium by the SOMC Strategy: Synthesis, Characterization and Structure-Activity Relationship in Ethylene Oligomerization Reaction

    KAUST Repository

    Hamieh, Ali Imad Ali

    2017-06-06

    Silica supported Tetramethyl niobium complex [(≡SiO)NbMe4] 2 has been isolated by surface alkylation of [(≡SiO-)NbCl3Me] 1 with dimethyl zinc in pentane. 1 can be easily synthesized by grafting of NbCl3Me2 on to the surface of partially dehydroxylated silica by the SOMC strategy. Precise structural analysis was carried out by the FTIR, advance solid state NMR, elemental analysis and mass balance techniques (gas quantification after treating 2 with degassed water) . Complex 1 was found to be active in the ethylene oligomerization to produce up to C30, whereas to our surprise complex 2 selectively dimerizes ethylene into 1-butene in the absence of a co-catalyst at the same conversion levels.

  3. Single Site Silica Supported Tetramethyl Niobium by the SOMC Strategy: Synthesis, Characterization and Structure-Activity Relationship in Ethylene Oligomerization Reaction

    KAUST Repository

    Hamieh, Ali Imad Ali; Dey, Raju; Nekoueishahraki, Bijan; Samantaray, Manoja; Chen, Yin; Abou-Hamad, Edy; Basset, Jean-Marie

    2017-01-01

    Silica supported Tetramethyl niobium complex [(≡SiO)NbMe4] 2 has been isolated by surface alkylation of [(≡SiO-)NbCl3Me] 1 with dimethyl zinc in pentane. 1 can be easily synthesized by grafting of NbCl3Me2 on to the surface of partially dehydroxylated silica by the SOMC strategy. Precise structural analysis was carried out by the FTIR, advance solid state NMR, elemental analysis and mass balance techniques (gas quantification after treating 2 with degassed water) . Complex 1 was found to be active in the ethylene oligomerization to produce up to C30, whereas to our surprise complex 2 selectively dimerizes ethylene into 1-butene in the absence of a co-catalyst at the same conversion levels.

  4. Nanostructured poly(benzimidazole membranes by N-alkylation

    Directory of Open Access Journals (Sweden)

    J. Weber

    2014-01-01

    Full Text Available Modification of poly(benzimidazole (PBI by N-alkylation leads to polymers capable of undergoing microphase separation. Polymers with different amounts of C18 alkyl chains have been prepared. The polymers were analyzed by spectroscopy, thermal analysis, electron microscopy and X-ray scattering. The impact of the amount of alkyl chains on the observed microphase separation was analyzed. Membranes prepared from the polymers do show microphase separation, as evidenced by scattering experiments. While no clear morphology could be derived for the domains in the native state, evidence for the formation of lamellar morphologies upon doping with phosphoric acid is provided. Finally, the proton conductivity of alkyl-modified PBI is compared with that of pure PBI, showing that the introduction of alkyl side chains does not result in significant conductivity changes.

  5. Aryl sulfonate based anticancer alkylating agents.

    Science.gov (United States)

    Sheikh, Hamdullah Khadim; Arshad, Tanzila; Kanwal, Ghazala

    2018-05-01

    This research work revolves around synthesis of antineoplastic alkylating sulfonate esters with dual alkylating sites for crosslinking of the DNA strands. These molecules were evaluated as potential antineoplastic cross linking alkylating agents by reaction with the nucleoside of Guanine DNA nucleobase at both ends of the synthesized molecule. Synthesis of the alkylating molecules and the crosslinking with the guanosine nucleoside was monitored by MALDITOF mass spectroscopy. The synthesized molecule's crosslinking or adduct forming rate with the nucleoside was compared with that of 1,4 butane disulfonate (busulfan), in form of time taken for the appearance of [M+H] + . It was found that aryl sulfonate leaving group was causing higher rate of nucleophilic attack by the Lewis basic site of the nucleobase. Furthermore, the rate was also found to be a function of electron withdrawing or donating nature of the substituent on the aryl ring. Compound with strong electron withdrawing substituent on the para position of the ring reacted fastest. Hence, new alkylating agents were synthesized with optimized or desired reactivity.

  6. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    Science.gov (United States)

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  7. Hydrothermal stability of silica, hybrid silica and Zr-doped hybrid silica membranes

    NARCIS (Netherlands)

    ten Hove, Marcel; Luiten-Olieman, Mieke W.J.; Huiskes, Cindy; Nijmeijer, Arian; Winnubst, Louis

    2017-01-01

    Hybrid silica membranes have demonstrated to possess a remarkable hydrothermal stability in pervaporation and gas separation processes allowing them to be used in industrial applications. In several publications the hydrothermal stability of pure silica or that of hybrid silica membranes are

  8. Fumed silica. Fumed silica

    Energy Technology Data Exchange (ETDEWEB)

    Sukawa, T.; Shirono, H. (Nippon Aerosil Co. Ltd., Tokyo (Japan))

    1991-10-18

    The fumed silica is explained in particulate superfineness, high purity, high dispersiveness and other remarkable characteristics, and wide application. The fumed silica, being presently produced, is 7 to 40nm in average primary particulate diameter and 50 to 380m{sup 2}/g in specific surface area. On the surface, there coexist hydrophilic silanol group (Si-OH) and hydrophobic siloxane group (Si-O-Si). There are many characteristics, mutually different between the fumed silica, made hydrophobic by the surface treatment, and untreated hydrophilic silica. The treated silica, if added to the liquid product, serves as agent to heighten the viscosity, prevent the sedimentation and disperse the particles. The highest effect is given to heighten the viscosity in a region of 4 to 9 in pH in water and alcohol. As filling agent to strengthen the elastomer and polymer, and powder product, it gives an effect to prevent the consolidation and improve the fluidity. As for its other applications, utilization is made of particulate superfineness, high purity, thermal insulation properties and adsorption characteristics. 2 to 3 patents are published for it as raw material of quartz glass. 38 refs., 16 figs., 4 tabs.

  9. The light activated alkylation of glycine

    International Nuclear Information System (INIS)

    Knowles, H.S.

    2001-04-01

    The work contained in this thesis focuses on the light-initiated alkylation of the α-centre of glycine compounds. The elaboration of the glycines in this manner represents a versatile, clean and cost effective alternative to ionic routes to higher α-amino acids. Preliminary investigations demonstrated that a range of nitrogen protecting groups were compatible with the radical alkylation. A variety of solvents could also be used although solvents with easily removable hydrogen atoms were found to interfere with the alkylation. Furthermore, a number of photo-initiators were investigated and the use of di-tert-butyl peroxide was found to afford the desired phenylalanine products in up to 27% yield (54% based on recovered starting material) when toluene was used as the alkylating agent. A range of different precursor concentrations was investigated and it was found that the optimum concentration of the glycine precursor was 0.13 mol dm -3 ; the phenylalanine yields were reduced when the concentration was less than this value. Owing to the poor UV absorption by di-tert-butyl peroxide, benzophenone (an effective photosensitiser) was added to the reaction mixture and this was shown to increase the alkylation yields. The ratio of reagents which produced the highest yield of phenylalanine products was found to be 1 : 5 : 5 : 10 for glycine : di-tert-butyl peroxide : benzophenone : toluene. This produced the phenylalanine product in up to 37% yield (57% based on recovered starting material). A number of substituents. (e.g. F, Cl etc.) could be attached to the aromatic ring of the toluene alkylating agent, affording substituted phenylalanines in 5 - 36% under these conditions. The formation of chiral phenylalanine products was probed by reacting glycine precursors bearing chiral auxiliaries. However, low diastereoselectivities were observed; the d.r. ranged from 1 : 1.1 to 1 : 1.5 only when chiral ester and amide protecting groups were used. In the final chapter, the α-alkylation

  10. Amino acid nitrosation products as alkylating agents.

    Science.gov (United States)

    García-Santos, M del P; Calle, E; Casado, J

    2001-08-08

    Nitrosation reactions of alpha-, beta-, and gamma-amino acids whose reaction products can act as alkylating agents of DNA were investigated. To approach in vivo conditions for the two-step mechanism (nitrosation and alkylation), nitrosation reactions were carried out in aqueous acid conditions (mimicking the conditions of the stomach lumen) while the alkylating potential of the nitrosation products was investigated at neutral pH, as in the stomach lining cells into which such products can diffuse. These conclusions were drawn: (i) The alkylating species resulting from the nitrosation of amino acids with an -NH(2) group are the corresponding lactones; (ii) the sequence of alkylating power is: alpha-lactones > beta-lactones > gamma-lactones, coming respectively from the nitrosation of alpha-, beta-, and gamma-amino acids; and (iii) the results obtained may be useful in predicting the mutagenic effectiveness of the nitrosation products of amino acids.

  11. Heavy metal adsorptivity of calcium-alginate-modified diethylenetriamine-silica gel and its application to a flow analytical system using flame atomic absorption spectrometry

    International Nuclear Information System (INIS)

    Mori, Masanobu; Suzuki, Toshinobu; Sugita, Tsuyoshi; Nagai, Daisuke; Hirayama, Kazuo; Onozato, Makoto; Itabashi, Hideyuki

    2014-01-01

    Highlights: • Calcium-alginate-modified dien-silica gel adsorbed multivalent metal ions. • Metal ions adsorbed on CaAD were eluted using low acidic concentrations. • Flow system with CaAD-packed column enriched metal concentrations up to 50-fold. - Abstract: This study aimed to evaluate the heavy metal adsorptivity of calcium-alginate-modified diethylenetriamine-silica gel (CaAD) and incorporate this biosorbent into a flow analytical system for heavy metal ions using flame atomic absorption spectrometry (FAAS). The biosorbent was synthesized by electrostatically coating calcium alginate onto diethylenetriamine (dien)-silica gel. Copper ion adsorption tests by a batch method showed that CaAD exhibited a higher adsorption rate compared with other biosorbents despite its low maximum adsorption capacity. Next, CaAD was packed into a 1 mL microcolumn, which was connected to a flow analytical system equipped with an FAAS instrument. The flow system quantitatively adsorbed heavy metals and enriched their concentrations. This quantitative adsorption was achieved for pH 3–4 solutions containing 1.0 × 10 −6 M of heavy metal ions at a flow rate of 5.0 mL min −1 . Furthermore, the metal ions were successfully desorbed from CaAD at low nitric acid concentrations (0.05–0.15 M) than from the polyaminecarboxylic acid chelating resin (Chelex 100). Therefore, CaAD may be considered as a biosorbent that quickly adsorbs and easily desorbs analyte metal ions. In addition, the flow system enhanced the concentrations of heavy metals such as Cu 2+ , Zn 2+ , and Pb 2+ by 50-fold. This new enrichment system successfully performed the separation and determination of Cu 2+ (5.0 × 10 −8 M) and Zn 2+ (5.7 × 10 −8 M) in a river water sample and Pb 2+ (3.8 × 10 −9 M) in a ground water sample

  12. N-Alkylation by Hydrogen Autotransfer Reactions.

    Science.gov (United States)

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed.

  13. Preparation of trialkylindium by alkylation of metallic indium

    International Nuclear Information System (INIS)

    Eremeev, I.V.; Danov, S.M.; Sakhipov, V.R.

    1995-01-01

    The investigation results on production of trialkyl indium by alkylation of metallic indium are presented. In contradistinction to the known techniques for the production of trialkyls on indium by alkylation it is suggested to separate the synthesis into two steps. At the first step indium is alkylated by alkylhalide to alkyl indium halide, and at the second alkylation is carried out using. Grignard reagent. The techniques for preparation of trimethyl- and triethylindium, developed on the bases of this scheme, are noted for good reproducibility, allow to preclude, agglomeration of indium during the synthesis, as well as to reduce the consumption coefficients, and amounts, of the introduced starting reagents, i.e. magnesium and alkylhalide. Refs. 16

  14. Insignificant influence of the matrix on the melting of ice confined in decorated mesoporous silica

    Science.gov (United States)

    Xu, Yunbo; Zhao, Zhenyan; Wang, Lianwen

    2018-01-01

    For a critical examination of matrix effect on the melting of confined ice, mesoporous silica (SBA-15) are synthesised and decorated with n-Alkyl and aminopropyl groups to tune the surface hydrophobicity. Water contact angle to these decorated surfaces are estimated to be about 100° and 60°, respectively. By examining the melting of ice confined in these decorated samples, we find that the influence of the matrix is indeed not significant. The reported apparent matrix effect is more likely method effect in the determination of pore diameters as was demonstrated in our previous studies (Philos. Mag. 93 (2013), p. 1827).

  15. Arrays of 3D micro-columns generated by laser ablation of Ta and steel: modelling of a black body emitter

    Energy Technology Data Exchange (ETDEWEB)

    Bensaoula, A.; Boney, C.; Pillai, R.; Starikov, D. [Texas Center for Superconductivity and Advanced Materials, University of Houston, Houston, TX (United States); Shafeev, G.A.; Simakin, A.V. [Wave Research Center, General Physics Institute of the Russian Academy of Sciences, 38, Vavilov Street, 119991, Moscow (Russian Federation)

    2004-09-01

    Three-dimensional extended arrays of micro-columns are generated on the surface of Ta and several stainless steels by their ablation by radiation of a Cu vapor laser either in vacuum or in air. The reflectivity of the arrays is tested in both visible and near-IR regions using the facilities at NASA Johnson Space Center. The reflectivity of the laser-treated areas was found to be very low (0.03-0.08) in the range 250-2800 nm. The emissivity of 3D arrays measured at elevated temperatures is close to the emissivity of a calibrated black body emitter. The effects of the experimental conditions of ablation (laser fluence, environment, etc.) on the integral optical characteristics of the generated arrays are discussed. (orig.)

  16. Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application

    KAUST Repository

    Hamzaoui, Bilel

    2016-01-27

    Single-site, well-defined, silica-supported tantallaaziridine intermediates [≡Si-O-Ta(η2-NRCH2)(NMe2)2] [R=Me (2), Ph (3)] were prepared from silica-supported tetrakis(dimethylamido)tantalum [≡Si-O-Ta(NMe2)4] (1) and fully characterized by FTIR spectroscopy, elemental analysis, and 1H,13C HETCOR and DQ TQ solid-state (SS) NMR spectroscopy. The formation mechanism, by β-H abstraction, was investigated by SS NMR spectroscopy and supported by DFT calculations. The C-H activation of the dimethylamide ligand is favored for R=Ph. The results from catalytic testing in the hydroaminoalkylation of alkenes were consistent with the N-alkyl aryl amine substrates being more efficient than N-dialkyl amines. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Sorbate-nitrite interactions: acetonitrile oxide as an alkylating agent.

    Science.gov (United States)

    Pérez-Prior, M Teresa; Gómez-Bombarelli, Rafael; González-Pérez, Marina; Manso, José A; García-Santos, M Pilar; Calle, Emilio; Casado, Julio

    2009-07-01

    Because chemical species with DNA-damaging and mutagenic activity are formed in sorbate-nitrite mixtures and because sorbic acid sometimes coexists with nitrite occurring naturally or incorporated as a food additive, the study of sorbate-nitrite interactions is important. Here, the alkylating potential of the products resulting from such interactions was investigated. Drawn were the following conclusions: (i) Acetonitrile oxide (ACNO) is the compound responsible for the alkylating capacity of sorbate-nitrite mixtures; (ii) ACNO alkylates 4-(p-nitrobenzyl)pyridine (NBP), a trap for alkylating agents with nucleophilic characteristics similar to those of DNA bases, forming an adduct (AD; epsilon = 1.4 x 10(4) M(-1) cm(-1); lambda = 519 nm); (iii) the NBP alkylation reaction complies with the rate equation, r = d[AD]/dt = k(alk)(ACNO)[ACNO][NBP]-k(hyd)(AD)[AD], k(alk)(ACNO) being the NBP alkylation rate constant for ACNO and k(hyd)(AD) the rate constant for the adduct hydrolysis reaction; (iv) the small fraction of ACNO forming the adduct with NBP, as well as the small magnitude of the quotient (k(alk) (ACNO)/k(hyd)(ACNO)) as compared with those reported for other alkylating agents, such as some lactones and N-alkyl-N-nitrosoureas, reveals the ACNO effective alkylating capacity to be less significant; (v) the low value of the NBP-ACNO adduct life (defined as the total amount of adduct present along the progression of the NBP alkylation per unit of alkylating agent concentration) points to the high instability of this adduct; and (vi) the obtained results are in accordance with the low carcinogenicity of ACNO.

  18. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl amino nitriles (generic). 721... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96...

  19. The formation of quasi-alicyclic rings in alkyl-aromatic compounds

    Science.gov (United States)

    Straka, Pavel; Buryan, Petr; Bičáková, Olga

    2018-02-01

    The alkyl side chains of n-alkyl phenols, n-alkyl benzenes and n-alkyl naphthalenes are cyclised, as demonstrated by GC measurements, FTIR spectroscopy and molecular mechanics calculations. Cyclisation occurs due to the intramolecular interaction between an aromatic ring (-δ) and a hydrogen of the terminal methyl group (+δ) of an alkyl chain. In fact, conventional molecules are not aliphatic-aromatic, but quasi-alicyclic-aromatic. With the aromatic molecules formed with a quasi-alicyclic ring, the effect of van der Waals attractive forces increases not only intramolecularly but also intermolecularly. This effect is strong in molecules with propyl and higher alkyl substituents. The increase of intermolecular van der Waals attractive forces results in bi-linearity in the GC retention time of the compounds in question, observed in the dependence of the logarithm of the relative retention time on the number of carbons in a molecule in both polar and nonpolar stationary phases with both capillary and packed columns. The role of van der Waals forces has been demonstrated using the potential energies of covalent and noncovalent interactions for 2-n-alkyl phenols, n-alkyl benzenes and 1-n-alkyl- and 2-n-alkyl naphthalenes.

  20. Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines.

    Science.gov (United States)

    Sakamoto, Ryu; Sakurai, Shunya; Maruoka, Keiji

    2017-07-06

    The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Alkylation of N-substituted 2-phenylacetamides

    Directory of Open Access Journals (Sweden)

    SLOBODAN D. PETROVIC

    2004-10-01

    Full Text Available Various N-substituted phenylacetamides were alkylated using different alkylating agents under neutral and basic conditions. Reactions were performed at different reaction temperatures and in various solvents. Also, a number of various catalysts were used including phase-transfer catalysts. Reactions were followed using GC or GC-MS technique and the presence as well as the yields of the alkylation products were established. Generally, the best yield and high selectivity in the studied reactions were achieved under basic conditions where in the certain cases some products, mostly N-product, were obtained solely in quantitative yields.

  2. Alkylation damage by lipid electrophiles targets functional protein systems.

    Science.gov (United States)

    Codreanu, Simona G; Ullery, Jody C; Zhu, Jing; Tallman, Keri A; Beavers, William N; Porter, Ned A; Marnett, Lawrence J; Zhang, Bing; Liebler, Daniel C

    2014-03-01

    Protein alkylation by reactive electrophiles contributes to chemical toxicities and oxidative stress, but the functional impact of alkylation damage across proteomes is poorly understood. We used Click chemistry and shotgun proteomics to profile the accumulation of proteome damage in human cells treated with lipid electrophile probes. Protein target profiles revealed three damage susceptibility classes, as well as proteins that were highly resistant to alkylation. Damage occurred selectively across functional protein interaction networks, with the most highly alkylation-susceptible proteins mapping to networks involved in cytoskeletal regulation. Proteins with lower damage susceptibility mapped to networks involved in protein synthesis and turnover and were alkylated only at electrophile concentrations that caused significant toxicity. Hierarchical susceptibility of proteome systems to alkylation may allow cells to survive sublethal damage while protecting critical cell functions.

  3. Alkylation Damage by Lipid Electrophiles Targets Functional Protein Systems*

    Science.gov (United States)

    Codreanu, Simona G.; Ullery, Jody C.; Zhu, Jing; Tallman, Keri A.; Beavers, William N.; Porter, Ned A.; Marnett, Lawrence J.; Zhang, Bing; Liebler, Daniel C.

    2014-01-01

    Protein alkylation by reactive electrophiles contributes to chemical toxicities and oxidative stress, but the functional impact of alkylation damage across proteomes is poorly understood. We used Click chemistry and shotgun proteomics to profile the accumulation of proteome damage in human cells treated with lipid electrophile probes. Protein target profiles revealed three damage susceptibility classes, as well as proteins that were highly resistant to alkylation. Damage occurred selectively across functional protein interaction networks, with the most highly alkylation-susceptible proteins mapping to networks involved in cytoskeletal regulation. Proteins with lower damage susceptibility mapped to networks involved in protein synthesis and turnover and were alkylated only at electrophile concentrations that caused significant toxicity. Hierarchical susceptibility of proteome systems to alkylation may allow cells to survive sublethal damage while protecting critical cell functions. PMID:24429493

  4. Alkylating agents for Waldenstrom's macroglobulinaemia.

    Science.gov (United States)

    Yang, Kun; Tan, Jianlong; Wu, Taixiang

    2009-01-21

    Waldenstrom's macroglobulinaemia (WM) is an uncommon B-cell lymphoproliferative disorder characterized by bone marrow infiltration and production of monoclonal immunoglobulin. Uncertainty remains if alkylating agents, such as chlorambucil, melphalan or cyclophosphamide, are an effective form of management. To assess the effects and safety of the alkylating agents on Waldenstrom's macroglobulinaemia (WM). We searched the Cochrane Central Register of Controlled Trials (Issue 1, 2008), MEDLINE (1966 to 2008), EMBASE (1980 to 2008), the Chinese Biomedical Base (1982 to 2008) and reference lists of articles.We also handsearched relevant conference proceedings from 1990 to 2008. Randomised controlled trials (RCTs) comparing alkylating agents given concomitantly with radiotherapy, splenectomy, plasmapheresis, stem-cell transplantation in patients with a confirmed diagnosis of WM. Two authors independently assessed trial quality and extracted data. We contacted study authors for additional information. We collected adverse effects information from the trials. One trial involving 92 participants with pretreated/relapsed WM compared the effect of fludarabine versus the combination of cyclophosphamide (the alkylating agent), doxorubicin and prednisone (CAP). Compared to CAP, the Hazard ratio (HR) for deaths of treatment with fludarabine was estimated to be 1.04, with a standard error of 0.30 (95% CI 0.58 to 1.48) and it indicated that the mean difference of median survival time was -4.00 months, and 16.00 months for response duration. The relative risks (RR) of response rate was 2.80 (95% CI 1.10 to 7.12). There were no statistically difference in overall survival rate and median survival months, while on the basis of response rate and response duration, fludarabine seemed to be superior to CAP for pretreated/relapsed patients with macroglobulinaemia. Although alkylating agents have been used for decades they have never actually been tested in a proper randomised trial. This

  5. Highly efficient proteome analysis with combination of protein pre-fractionation by preparative microscale solution isoelectric focusing and identification by μRPLC-MS/MS with serially coupled long microcolumn.

    Science.gov (United States)

    Tao, Dingyin; Sun, Liangliang; Zhu, Guijie; Liang, Yu; Liang, Zhen; Zhang, Lihua; Zhang, Yukui

    2011-01-01

    To improve the efficiency of proteome analysis, a strategy with the combination of protein pre-fractionation by preparative microscale solution isoelectric focusing, peptide separation by μRPLC with serially coupled long microcolumn and protein identification by ESI-MS/MS was proposed. By preparative microscale solution isoelectric focusing technique, proteins extracted from whole cell lysates of Escherichia coli were fractionated into five chambers divided by isoelectric membranes, respectively with pH range from 3.0 to 4.6, 4.6 to 5.4, 5.4 to 6.2, 6.2 to 7.0 and 7.0 to 10.0. Compared to the traditional on-gel IFF, the protein recovery could be obviously improved to over 95%. Subsequently, the enriched and fractionated proteins in each chamber were digested, and further separated by a 30-cm long serially coupled RP microcolumn. Through the detection by ESI-MS/MS, about 200 proteins were identified in each fraction, and in total 835 proteins were identified even with one-dimensional μRPLC-MS/MS system. All these results demonstrate that by such a combination strategy, highly efficient proteome analysis could be achieved, not only due to the in-solution protein enrichment and pre-fractionation with improved protein recovery but also owing to the increased separation capacity of serially coupled long μRPLC columns. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Micro-Columnated Loop Heat Pipe: The Future of Electronic Substrates

    Science.gov (United States)

    Dhillon, Navdeep Singh

    The modern world is run by semiconductor-based electronic systems. Due to continuous improvements in semiconductor device fabrication, there is a clear trend in the market towards the development of electronic devices and components that not only deliver enhanced computing power, but are also more compact. Thermal management has emerged as the primary challenge in this scenario where heat flux dissipation of electronic chips is increasing exponentially, but conventional cooling solutions such as conduction and convection are no longer feasible. To keep device junction temperatures within the safe operating limit, there is an urgent requirement for ultra-high-conductivity thermal substrates that not only absorb and transport large heat fluxes, but can also provide localized cooling to thermal hotspots. This dissertation describes the design, modeling, and fabrication of a phase change-based, planar, ultra-thin, passive thermal transport system that is inspired by the concept of loop heat pipes and capillary pumped loops. Fabricated on silicon and Pyrex wafers using microfabrication techniques, the micro-columnated loop heat pipe (muCLHP) can be integrated directly with densely packed or multiply-stacked electronic substrates, to provide localized high-heat-flux thermal management. The muCLHP employs a dual-scale coherent porous silicon(CPS)-based micro-columnated wicking structure, where the primary CPS wick provides large capillary forces for fluid transport, while a secondary surface-wick maximizes the rate of thin-film evaporation. To overcome the wick thickness limitation encountered in conventional loop heat pipes, strategies based on MEMS surface micromachining techniques were developed to reduce parasitic heat flow from the evaporator to the compensation chamber of the device. Finite element analysis was used to confirm this reduction in a planar evaporator design, thus enabling the generation of a large motive temperature head for continuous device operation

  7. Quantitative structure–activity relationships for chronic toxicity of alkyl-chrysenes and alkyl-benz[a]anthracenes to Japanese medaka embryos (Oryzias latipes)

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Hongkang [Department of Biology, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Morandi, Garrett D. [School of Environmental Studies, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Brown, R. Stephen [School of Environmental Studies, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Department of Chemistry, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Snieckus, Victor; Rantanen, Toni [Department of Chemistry, Queen' s University, Kingston, Ontario K7L3N6 (Canada); Jørgensen, Kåre B. [Department of Mathematics and Natural Sciences, University of Stavanger, 4036 Stavanger (Norway); Hodson, Peter V., E-mail: peter.hodson@queensu.ca [Department of Biology, Queen' s University, Kingston, Ontario K7L3N6 (Canada); School of Environmental Studies, Queen' s University, Kingston, Ontario K7L3N6 (Canada)

    2015-02-15

    Highlights: • Medaka embryos were exposed to alkyl chrysenes and benzo[a]anthracenes (BAA). • Concentrations were kept constant by partition controlled delivery. • Chrysene was not toxic within solubility limits, in contrast to BAA. • Alkylation increased the toxicity of chrysene and BAA. • Toxicity was related to hydrophobicity and to specific modes of action. - Abstract: Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) are a class of compounds found at significant concentrations in crude oils, and likely the main constituents responsible for the chronic toxicity of oil to fish. Alkyl substituents at different locations on the aromatic rings change the size and shape of PAH molecules, which results in different interactions with tissue receptors and different severities of toxicity. The present study is the first to report the toxicity of several alkylated derivatives of chrysene and benz[a]anthracene to the embryos of Japanese medaka (Oryzias latipes) using the partition controlled delivery (PCD) method of exposure. The PCD method maintained the desired exposure concentrations by equilibrium partitioning of hydrophobic test compounds from polydimethylsiloxane (PDMS) films. Test concentrations declined by only 13% over a period of 17 days. Based on the prevalence of signs of blue sac disease (BSD), as expressed by median effective concentrations (EC50s), benz[a]anthracene (B[a]A) was more toxic than chrysene. Alkylation generally increased toxicity, except at position 2 of B[a]A. Alkyl-PAHs substituted in the middle region had a lower EC50 than those substituted at the distal region. Except for B[a]A and 7-methylbenz[a]anthracene (7-MB), estimated EC50 values were higher than their solubility limits, which resulted in limited toxicity within the range of test concentrations. The regression between log EC50s and log K{sub ow} values provided a rough estimation of structure–activity relationships for alkyl-PAHs, but K{sub ow} alone did not provide

  8. Development of novel alkylating drugs as anticancer agents.

    Science.gov (United States)

    Izbicka, Elzbieta; Tolcher, Anthony W

    2004-06-01

    Although conventional alkylating drugs have proven efficacy in the treatment of malignancies, the agents themselves are not selective. Therefore, non-specific alkylation of cellular nucleophilic targets may contribute to many of the observed toxic effects. Novel approaches to drug discovery have resulted in candidate agents that are focused on 'soft alkylation'--alkylators with greater target selectivity. This review highlights the discovery of small molecule drugs that bind to DNA with higher selectivity, act in a unique hypoxic tumor environment, or covalently bind specific protein targets overexpressed in cancer, such as topoisomerase II, glutathione transferase pi1, beta-tubulin and histone deacetylase.

  9. Mechanochemical N-alkylation of imides

    Directory of Open Access Journals (Sweden)

    Anamarija Briš

    2017-08-01

    Full Text Available The mechanochemical N-alkylation of imide derivatives was studied. Reactions under solvent-free conditions in a ball mill gave good yields and could be put in place of the classical solution conditions. The method is general and can be applied to various imides and alkyl halides. Phthalimides prepared under ball milling conditions were used in a mechanochemical Gabriel synthesis of amines by their reaction with 1,2-diaminoethane.

  10. Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite

    Science.gov (United States)

    Cooper, George W.; Onwo, Wilfred M.; Cronin, John R.

    1992-01-01

    Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, are identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl derivatives. The methyl, ethyl, propyl, and butyl compounds are observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 are identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in the alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series.

  11. Immobilization of lipases on alkyl silane modified magnetic nanoparticles: effect of alkyl chain length on enzyme activity.

    Directory of Open Access Journals (Sweden)

    Jiqian Wang

    Full Text Available BACKGROUND: Biocatalytic processes often require a full recycling of biocatalysts to optimize economic benefits and minimize waste disposal. Immobilization of biocatalysts onto particulate carriers has been widely explored as an option to meet these requirements. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work is to explore how immobilization of lipases onto magnetite nanoparticles affects their biocatalytic performance under carefully controlled surface modification. METHODOLOGY/PRINCIPAL FINDINGS: Magnetite nanoparticles, prepared through a co-precipitation method, were coated with alkyl silanes of different alkyl chain lengths to modulate their surface hydrophobicity. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through hydrophobic interaction. Enzyme activity was assessed by catalytic hydrolysis of p-nitrophenyl acetate. The activity of immobilized lipases was found to increase with increasing chain length of the alkyl silane. Furthermore, the catalytic activities of lipases immobilized on trimethoxyl octadecyl silane (C18 modified Fe(3O(4 were a factor of 2 or more than the values reported from other surface immobilized systems. After 7 recycles, the activities of the lipases immobilized on C18 modified nanoparticles retained 65%, indicating significant enhancement of stability as well through hydrophobic interaction. Lipase immobilized magnetic nanoparticles facilitated easy separation and recycling with high activity retaining. CONCLUSIONS/SIGNIFICANCE: The activity of immobilized lipases increased with increasing alkyl chain length of the alkyl trimethoxy silanes used in the surface modification of magnetite nanoparticles. Lipase stability was also improved through hydrophobic interaction. Alkyl silane modified magnetite nanoparticles are thus highly attractive carriers for

  12. Immobilization of lipases on alkyl silane modified magnetic nanoparticles: effect of alkyl chain length on enzyme activity.

    Science.gov (United States)

    Wang, Jiqian; Meng, Gang; Tao, Kai; Feng, Min; Zhao, Xiubo; Li, Zhen; Xu, Hai; Xia, Daohong; Lu, Jian R

    2012-01-01

    Biocatalytic processes often require a full recycling of biocatalysts to optimize economic benefits and minimize waste disposal. Immobilization of biocatalysts onto particulate carriers has been widely explored as an option to meet these requirements. However, surface properties often affect the amount of biocatalysts immobilized, their bioactivity and stability, hampering their wide applications. The aim of this work is to explore how immobilization of lipases onto magnetite nanoparticles affects their biocatalytic performance under carefully controlled surface modification. Magnetite nanoparticles, prepared through a co-precipitation method, were coated with alkyl silanes of different alkyl chain lengths to modulate their surface hydrophobicity. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through hydrophobic interaction. Enzyme activity was assessed by catalytic hydrolysis of p-nitrophenyl acetate. The activity of immobilized lipases was found to increase with increasing chain length of the alkyl silane. Furthermore, the catalytic activities of lipases immobilized on trimethoxyl octadecyl silane (C18) modified Fe(3)O(4) were a factor of 2 or more than the values reported from other surface immobilized systems. After 7 recycles, the activities of the lipases immobilized on C18 modified nanoparticles retained 65%, indicating significant enhancement of stability as well through hydrophobic interaction. Lipase immobilized magnetic nanoparticles facilitated easy separation and recycling with high activity retaining. The activity of immobilized lipases increased with increasing alkyl chain length of the alkyl trimethoxy silanes used in the surface modification of magnetite nanoparticles. Lipase stability was also improved through hydrophobic interaction. Alkyl silane modified magnetite nanoparticles are thus highly attractive carriers for enzyme immobilization enabling efficient enzyme recovery and recycling.

  13. Evaluation of ionic liquids supported on silica as a sorbent for fully automated online solid-phase extraction with LC-MS determination of sulfonamides in bovine milk samples.

    Science.gov (United States)

    da Silva, Meire Ribeiro; Mauro Lanças, Fernando

    2018-03-10

    Sulfonamides are antibiotics widely used in the treatment of diseases in dairy cattle. However, their indiscriminate use for disease control may lead to their presence in tissues and milk and their determination requires a sample preparation step as part of an analytical approach. Among the several sample preparation techniques available, those based upon the use of sorptive materials have been widely employed. Recently, the application of ionic liquids immobilized on silica surfaces or polymeric materials has been evaluated for such an application. This manuscript addresses the evaluation of silica-based ionic liquid obtained by a sol-gel synthesis process by basic catalysis as sorbent for online solid-phase extraction with liquid chromatography and electrospray ionization time-of-flight mass spectrometry for sulfonamides determination. Infrared vibrational spectroscopy confirmed the presence of the ionic liquid on the silica surface, suggesting that the ionic liquid was anchored on to the silica surface. Other sorbents varying the ionic liquid alkyl chain were also synthesized and evaluated by off-line solid-phase extraction in the sulfonamide extraction. As the length of the alkyl chain increased, the amount of extracted sulfonamides decreased, possibly due to a decrease in the electrostatic interaction caused by the reduction in the polarity, as well as the presence of a hexafluorophosphate anion that increases the hydrophobic character of the material. The use of 1-butyl-3-methylimidazolium hexafluorophosphate as a selective ionic liquid sorbent enabled the isolation and sulfonamide preconcentration in bovine milk by online solid-phase extraction with liquid chromatography and electrospray ionization time-of-flight mass spectrometry. The limit of quantification for the method developed was 5-7, 5 μg/mL, with extraction recoveries ranging between 74 and 93% and intra- and interassay between 1.5-12.5 and 2.3-13.1, respectively. © 2018 WILEY-VCH Verlag Gmb

  14. DNA minor groove alkylating agents.

    Science.gov (United States)

    Denny, W A

    2001-04-01

    Recent work on a number of different classes of anticancer agents that alkylate DNA in the minor groove is reviewed. There has been much work with nitrogen mustards, where attachment of the mustard unit to carrier molecules can change the normal patterns of both regio- and sequence-selectivity, from reaction primarily at most guanine N7 sites in the major groove to a few adenine N3 sites at the 3'-end of poly(A/T) sequences in the minor groove. Carrier molecules discussed for mustards are intercalators, polypyrroles, polyimidazoles, bis(benzimidazoles), polybenzamides and anilinoquinolinium salts. In contrast, similar targeting of pyrrolizidine alkylators by a variety of carriers has little effect of their patterns of alkylation (at the 2-amino group of guanine). Recent work on the pyrrolobenzodiazepine and cyclopropaindolone classes of natural product minor groove binders is also reviewed.

  15. IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

    Science.gov (United States)

    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  16. Mass spectrometric protein characterization in proteome analysis using GELoader tip micro-columns packed with various chromatographic material

    International Nuclear Information System (INIS)

    Larsen, M.R.

    2001-01-01

    In the early 90'ies mass spectrometry (MS) was introduced as a tool for identifying proteins in protein sequence databases. Since then it has become an integrated tool in protein characterization and is today routinely used to identify proteins separated by gel electrophoresis. A two-tiered mass spectrometric protein identification strategy has recently been proposed. In the first strategy peptide mass maps obtained from the protein of interest are compared with theoretically derived peptide mass maps from proteins in protein sequence databases. If the protein cannot be identified by this strategy, tandem mass spectrometric sequencing is used to generate enough sequence data to identify the protein in protein sequence databases or expressed sequence tag (EST) databases. However, the above strategies primarily identify a protein relatively to the DNA sequence, in which no information about e.g. post-translational modifications (PTMs) is stored. PTMs are known to modify the function, location, solubility and activity of proteins in the cell, and they are therefore very important for understanding living cells. More than 200 different PTMs are known, of which glycosylation, phosphorylation and proteolytic processing are the most common ones. Mass spectrometric analysis of PTMs on gel-separated proteins requires a higher amount of protein than for identification only. In addition, higher sequence coverage from the peptide mass maps or pre-purification of the modified peptides prior to MS analysis, is necessary for detection of putative modified peptides. In this study a multi-tiered strategy, in which GELoader tip micro-columns packed with increasingly more hydrophobic chromatographic material are used in combination with mass spectrometry, is described. The ultimate aim was to gain increased sequence coverage from peptide mixtures derived from gel-separated proteins, in order to locate modified peptides. Graphite powder is described as an alternative to traditional

  17. Quantitative structure-activity relationships for chronic toxicity of alkyl-chrysenes and alkyl-benz[a]anthracenes to Japanese medaka embryos (Oryzias latipes).

    Science.gov (United States)

    Lin, Hongkang; Morandi, Garrett D; Brown, R Stephen; Snieckus, Victor; Rantanen, Toni; Jørgensen, Kåre B; Hodson, Peter V

    2015-02-01

    Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) are a class of compounds found at significant concentrations in crude oils, and likely the main constituents responsible for the chronic toxicity of oil to fish. Alkyl substituents at different locations on the aromatic rings change the size and shape of PAH molecules, which results in different interactions with tissue receptors and different severities of toxicity. The present study is the first to report the toxicity of several alkylated derivatives of chrysene and benz[a]anthracene to the embryos of Japanese medaka (Oryzias latipes) using the partition controlled delivery (PCD) method of exposure. The PCD method maintained the desired exposure concentrations by equilibrium partitioning of hydrophobic test compounds from polydimethylsiloxane (PDMS) films. Test concentrations declined by only 13% over a period of 17 days. Based on the prevalence of signs of blue sac disease (BSD), as expressed by median effective concentrations (EC50s), benz[a]anthracene (B[a]A) was more toxic than chrysene. Alkylation generally increased toxicity, except at position 2 of B[a]A. Alkyl-PAHs substituted in the middle region had a lower EC50 than those substituted at the distal region. Except for B[a]A and 7-methylbenz[a]anthracene (7-MB), estimated EC50 values were higher than their solubility limits, which resulted in limited toxicity within the range of test concentrations. The regression between log EC50s and logKow values provided a rough estimation of structure-activity relationships for alkyl-PAHs, but Kow alone did not provide a complete explanation of the chronic toxicity of alkyl PAHs. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for the...

  19. Regioselective 1-N-Alkylation and Rearrangement of Adenosine Derivatives.

    Science.gov (United States)

    Oslovsky, Vladimir E; Drenichev, Mikhail S; Mikhailov, Sergey N

    2015-01-01

    Several methods for the preparation of some N(6)-substituted adenosines based on selective 1-N-alkylation with subsequent Dimroth rearrangement were developed. The proposed methods seem to be effective for the preparation of natural N(6)-isopentenyl- and N(6)-benzyladenosines, which are known to possess pronounced biological activities. Direct 1-N-alkylation of 2',3',5'-tri-O-acetyladenosine and 3',5'-di-O-acetyl-2'-deoxyadenosine with alkyl halides in N,N-dimethylformamide (DMF) in the presence of BaCO3 and KI gave 1-N-substituted derivatives with quantitative yields, whereas 1-N-alkylation of adenosine was accompanied by significant O-alkylation. Moreover, the reaction of trimethylsilyl derivatives of N(6)-acetyl-2',3',5'-tri-O-acetyladenosine and N(6)-acetyl-3',5'-di-O-acetyl-2'-deoxyadenosine with alkyl halides leads to the formation of the stable 1-N-substituted adenosines. Dimroth rearrangement of 1-N-substituted adenosines in aqueous ammonia yields pure N(6)-substituted adenosines.

  20. Process for production of an alkyl methacrylate

    NARCIS (Netherlands)

    Eastham, Graham Ronald; Johnson, David William; Fraaije, Marco; Winter, Remko

    2015-01-01

    A process for the production of an alkyl methacrylate, particularly methyl methacrylate, is provided, in which a Baeyer-Villiger Monooxygenase enzyme is used to convert an alkylisopropenylketone substrate to the relevant alkyl methacrylate by abnormal asymmetric oxygen insertion. The invention

  1. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...... for the development of allylic C-H alkylation into a widely applicable methodology, thus providing a means to enhance synthetic efficiency in these reactions....

  2. Cu(I)-Catalyzed Enantioselective Friedel-Crafts Alkylation of Indoles with 2-Aryl-N-sulfonylaziridines as Alkylating Agents.

    Science.gov (United States)

    Ge, Chen; Liu, Ren-Rong; Gao, Jian-Rong; Jia, Yi-Xia

    2016-07-01

    A highly enantioselective Friedel-Crafts alkylation of indoles with N-sulfonylaziridines as alkylating agents has been developed by utilizing the complex of Cu(CH3CN)4BF4/(S)-Segphos as a catalyst. A range of optically active tryptamine derivatives are obtained in good to excellent yields and enantioselectivities (up to >99% ee) via a kinetic resolution process.

  3. Alkylation of terminal alkynes with transient σ-alkylpalladium(II) complexes: a carboalkynylation route to alkyl-substituted alkynes.

    Science.gov (United States)

    Zhou, Ming-Bo; Huang, Xiao-Cheng; Liu, Yan-Yun; Song, Ren-Jie; Li, Jin-Heng

    2014-02-10

    A mild and general alkylation of terminal alkynes with transient σ-alkylpalladium(II) complexes for assembling alkyl-substituted alkynes is described. This method represents a new way to the use of transient σ-alkylpalladium(II) complexes in organic synthesis through 1,2-carboalkynylation of alkenes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. UV absorption spectra, kinetics and mechanism for alkyl and alkyl peroxy radicals originating from t-butyl alcohol

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Sehested, J.

    1994-01-01

    Alkyl and alkyl peroxy radicals from 1-butyl alcohol (TBA), HOC (CH3)2CH2. and HOC(CH3)2CH2O2. have been studied in the ps phase at 298 K. Two techniques were used: pulse radiolysis UV absorption to measure the spectra and kinetics, and long path-length Fourier transform infrared spectroscopy (FTIR...

  5. Oxidative Umpolung α‐Alkylation of Ketones

    DEFF Research Database (Denmark)

    Shneider, O. Svetlana; Pisarevsky, Evgeni; Fristrup, Peter

    2015-01-01

    We disclose a hypervalent iodine mediated α-alkylative umpolung reaction of carbonyl compounds with dialkylzinc as the alkyl source. The reaction is applicable to all common classes of ketones including 1,3-dicarbonyl compounds and regular ketones via their lithium enolates. The α...

  6. A Convenient Approach to Synthesizing Peptide C-Terminal N-Alkyl Amides

    Science.gov (United States)

    Fang, Wei-Jie; Yakovleva, Tatyana; Aldrich, Jane V.

    2014-01-01

    Peptide C-terminal N-alkyl amides have gained more attention over the past decade due to their biological properties, including improved pharmacokinetic and pharmacodynamic profiles. However, the synthesis of this type of peptide on solid phase by current available methods can be challenging. Here we report a convenient method to synthesize peptide C-terminal N-alkyl amides using the well-known Fukuyama N-alkylation reaction on a standard resin commonly used for the synthesis of peptide C-terminal primary amides, the PAL-PEG-PS (Peptide Amide Linker-polyethylene glycol-polystyrene) resin. The alkylation and oNBS deprotection were conducted under basic conditions and were therefore compatible with this acid labile resin. The alkylation reaction was very efficient on this resin with a number of different alkyl iodides or bromides, and the synthesis of model enkephalin N-alkyl amide analogs using this method gave consistently high yields and purities, demonstrating the applicability of this methodology. The synthesis of N-alkyl amides was more difficult on a Rink amide resin, especially the coupling of the first amino acid to the N-alkyl amine, resulting in lower yields for loading the first amino acid onto the resin. This method can be widely applied in the synthesis of peptide N-alkyl amides. PMID:22252422

  7. Silica Nephropathy

    Directory of Open Access Journals (Sweden)

    N Ghahramani

    2010-06-01

    Full Text Available Occupational exposure to heavy metals, organic solvents and silica is associated with a variety of renal manifestations. Improved understanding of occupational renal disease provides insight into environmental renal disease, improving knowledge of disease pathogenesis. Silica (SiO2 is an abundant mineral found in sand, rock, and soil. Workers exposed to silica include sandblasters, miners, quarry workers, masons, ceramic workers and glass manufacturers. New cases of silicosis per year have been estimated in the US to be 3600–7300. Exposure to silica has been associated with tubulointerstitial disease, immune-mediated multisystem disease, chronic kidney disease and end-stage renal disease. A rare syndrome of painful, nodular skin lesions has been described in dialysis patients with excessive levels of silicon. Balkan endemic nephropathy is postulated to be due to chronic intoxication with drinking water polluted by silicates released during soil erosion. The mechanism of silica nephrotoxicity is thought to be through direct nephrotoxicity, as well as silica-induced autoimmune diseases such as scleroderma and systemic lupus erythematosus. The renal histopathology varies from focal to crescentic and necrotizing glomerulonephritis with aneurysm formation suggestive of polyarteritis nodosa. The treatment for silica nephrotoxicity is non-specific and depends on the mechanism and stage of the disease. It is quite clear that further research is needed, particularly to elucidate the pathogenesis of silica nephropathy. Considering the importance of diagnosing exposure-related renal disease at early stages, it is imperative to obtain a thorough occupational history in all patients with renal disease, with particular emphasis on exposure to silica, heavy metals, and solvents.

  8. Alkylation of Zwitterionic Thiooxalic Acid Derivatives

    Directory of Open Access Journals (Sweden)

    Manfred Michalik

    2001-05-01

    Full Text Available The new S-alkyl thiooxal-1-hydrazono-2-amidrazonium halides 2-4 were synthesized by reaction of the corresponding zwitterionic thiooxalic acid derivatives 1 with alkyl halides in methanol. The structures of compounds 4b and 4d were proven by X-ray structural analysis. Both compounds form an interesting intermolecular network of hydrogen bonds in the solid state.

  9. Antioxidant activity of alkyl gallates and glycosyl alkyl gallates in fish oil in water emulsions: relevance of their surface active properties and of the type of emulsifier.

    Science.gov (United States)

    González, María J; Medina, Isabel; Maldonado, Olivia S; Lucas, Ricardo; Morales, Juan C

    2015-09-15

    The antioxidant activity of gallic acid and a series of alkyl gallates (C4-C18) and glycosylated alkyl gallates (C4-C18) on fish oil-in-water emulsions was studied. Three types of emulsifiers, lecithin, Tween-20 and sodium dodecyl sulphate (SDS) were tested. A nonlinear behavior of the antioxidant activity of alkyl gallates when increasing alkyl chain length was observed for emulsions prepared with lecithin. Medium-size alkyl gallates (C6-C12) were the best antioxidants. In contrast, for emulsions prepared with Tween-20, the antioxidants seem to follow the polar paradox. Glucosyl alkyl gallates were shown previously to be better surfactants than alkyl gallates. Nevertheless, they exhibited a worse antioxidant capacity than their corresponding alkyl gallates, in emulsions prepared with lecithin or Tween-20, indicating the greater relevance of having three OH groups at the polar head in comparison with having improved surfactant properties but just a di-ortho phenolic structure in the antioxidant. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. UV absorption spectra and kinetics for alkyl and alkyl peroxy radicals originating from di-tert-butyl ether

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.; Langer, S.

    1995-01-01

    Alkyl, (CH3)(3)COC(CH3)(2)CH2, and alkyl peroxy, (CH3)(3)COC(CH3)(2)CH2O2, radicals from di-tert-butyl ether (DTBE), have been studied in the gas phase at 296 K. A pulse radiolysis UV absorption technique was used to measure the spectra and kinetics. Absorption cross sections were quantified over...

  11. Dynamics of cyanophenyl alkylbenzoate molecules in the bulk and in a surface layer adsorbed onto aerosil. Variation of the lengths of the alkyl chain

    Energy Technology Data Exchange (ETDEWEB)

    Frunza, Stefan [National Institute of Materials Physics, R-077125 Magurele (Romania); Schoenhals, Andreas [BAM Federal Institute of Materials Research and Testing, D-12205 Berlin (Germany); Frunza, Ligia, E-mail: lfrunza@infim.ro [National Institute of Materials Physics, R-077125 Magurele (Romania); Beica, Traian; Zgura, Irina; Ganea, Paul [National Institute of Materials Physics, R-077125 Magurele (Romania); Stoenescu, Daniel [Telecom-Bretagne, Departement d' Optique, Technopole Brest-Iroise 29238 Cedex (France)

    2010-06-16

    Graphical abstract: The temperature dependence of the molecular mobility in composites shows an Arrhenius-type regime at low temperature and a glassy-type one at higher temperature separated by a crossover phenomenon. - Abstract: The molecular mobility of 4-butyl- and 4-pentyl-4'-cyanophenyl benzoate (CP4B, CP5B) and their composites prepared from aerosil A380 was investigated by broadband dielectric spectroscopy in a large temperature range. Thermogravimetric and infrared investigations were additionally performed. High silica density (larger than 7 g aerosil/1 g of liquid crystal) was selected to observe a thin layer adsorbed on the surface of the silica particles. The data were compared with those of the member of the series with six carbon atoms in the alkyl tail. Bulk CP4B and CP5B show the dielectric behaviour expected for liquid crystals. For the composites one relaxation process is observed at frequencies much lower than those for the corresponding bulk, which was assigned to the dynamics of the molecules in a surface layer. The temperature dependence of the relaxation rates (and of the dielectric strength) shows a crossover behaviour with two distinguished regimes. At higher temperatures the data obey the Vogel-Fulcher-Tammann law, whereas an Arrhenius law is observed at lower temperature, in a close similarity to the behaviour of a constrained dynamic glass transition. The estimated Vogel and crossover temperature is independent on the tail length, while the activation energy for the low temperature branch increases weakly with increasing the alkyl tail.

  12. Visible light- and radiation-induced alkylation of pyridine ring with alkanoic acid

    International Nuclear Information System (INIS)

    Sugimori, Akira; Yamada, Tetsuo

    1986-01-01

    Quinoline and 4-methylquinoline are efficiently alkylated with alkanoic acid in the presence of iron(III) sulfate upon visible light-irradiation. Iron(III) sulfate not only accelerates the photoreaction but also increases the yield of alkylation. Gamma-irradiation also brings about the alkylation. In the photo- and radiation-induced alkylation with alkanoic acid, alkyl radicals play important roles. (author)

  13. General Allylic C–H Alkylation with Tertiary Nucleophiles

    Science.gov (United States)

    2015-01-01

    A general method for intermolecular allylic C–H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C–H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C–H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C–H reactivity are illustrated in an allylic C–H alkylation/Diels–Alder reaction cascade: a reactive diene is generated via intermolecular allylic C–H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids. PMID:24641574

  14. General allylic C-H alkylation with tertiary nucleophiles.

    Science.gov (United States)

    Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina

    2014-04-16

    A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

  15. Salvage of Failed Protein Targets by Reductive Alkylation

    Science.gov (United States)

    Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

    2014-01-01

    The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins. PMID:24590719

  16. Salvage of failed protein targets by reductive alkylation.

    Science.gov (United States)

    Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

    2014-01-01

    The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins.

  17. Predicting Alkylate Yield and its Hydrocarbon Composition for Sulfuric Acid Catalyzed Isobutane Alkylation with Olefins Using the Method of Mathematical Modeling

    OpenAIRE

    Nurmakanova, А. Е.; Ivashkina, Elena Nikolaevna; Ivanchina, Emilia Dmitrievna; Dolganov, I. A.; Boychenko, S. S.

    2015-01-01

    The article provides the results of applied mathematical model of isobutane alkylation with olefins catalyzed by sulfuric acid to predict yield and hydrocarbon composition of alkylate caused by the changes in the feedstock composition and process parameters. It is shown that the alkylate produced from feedstock with less mass fraction of isobutane has lower octane value. Wherein the difference in composition of the feedstock contributes to antiknock index by the amount of 1.0-2.0 points.

  18. Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes.

    Science.gov (United States)

    Di Franco, Thomas; Epenoy, Alexandre; Hu, Xile

    2015-10-02

    The first Ni-catalyzed Suzuki-Miyaura coupling of alkyl halides with alkenyl-(9-BBN) reagents is reported. Both primary and secondary alkyl halides including alkyl chlorides can be coupled. The coupling method can be combined with hydroboration of terminal alkynes, allowing the expedited synthesis of functionalized alkyl alkenes from readily available alkynes with complete (E)-selectivity in one pot. The method was applied to the total synthesis of (±)-Recifeiolide, a natural macrolide.

  19. Isobutane alkylation. Recent developments and future perspectives

    Energy Technology Data Exchange (ETDEWEB)

    Hommeltoft, Sven Ivar [Haldor Topsoe A/S, Nymoellevej 55, DK-2800 Lyngby (Denmark)

    2001-11-30

    In the isobutane alkylation, alkylated gasoline is obtained which is a valuable blending component for the gasoline pool. Thereby the C{sub 3}-C{sub 4} cut from the FCC units can be extensively used. Established technologies and recent developments will be reviewed and future perspectives will be given.

  20. Selective alkylation of T-T mismatched DNA using vinyldiaminotriazine-acridine conjugate.

    Science.gov (United States)

    Onizuka, Kazumitsu; Usami, Akira; Yamaoki, Yudai; Kobayashi, Tomohito; Hazemi, Madoka E; Chikuni, Tomoko; Sato, Norihiro; Sasaki, Kaname; Katahira, Masato; Nagatsugi, Fumi

    2018-02-16

    The alkylation of the specific higher-order nucleic acid structures is of great significance in order to control its function and gene expression. In this report, we have described the T-T mismatch selective alkylation with a vinyldiaminotriazine (VDAT)-acridine conjugate. The alkylation selectively proceeded at the N3 position of thymidine on the T-T mismatch. Interestingly, the alkylated thymidine induced base flipping of the complementary base in the duplex. In a model experiment for the alkylation of the CTG repeats DNA which causes myotonic dystrophy type 1 (DM1), the observed reaction rate for one alkylation increased in proportion to the number of T-T mismatches. In addition, we showed that primer extension reactions with DNA polymerase and transcription with RNA polymerase were stopped by the alkylation. The alkylation of the repeat DNA will efficiently work for the inhibition of replication and transcription reactions. These functions of the VDAT-acridine conjugate would be useful as a new biochemical tool for the study of CTG repeats and may provide a new strategy for the molecular therapy of DM1.

  1. Balancing repair and tolerance of DNA damage caused by alkylating agents.

    Science.gov (United States)

    Fu, Dragony; Calvo, Jennifer A; Samson, Leona D

    2012-01-12

    Alkylating agents constitute a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER) and mismatch repair (MMR), respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial for a favourable response of an organism to alkylating agents. Furthermore, the response of an individual to alkylating agents can vary considerably from tissue to tissue and from person to person, pointing to genetic and epigenetic mechanisms that modulate alkylating agent toxicity.

  2. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

    2013-10-01

    Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

  3. Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

    OpenAIRE

    Liu, Wen-Bo; Okamoto, Noriko; Alexy, Eric J.; Hong, Allen Y.; Tran, Kristy; Stoltz, Brian M.

    2016-01-01

    A catalytic, enantioselective ? -alkylation of ?,?-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed ?-alkylation of an extended enolate, and a subsequent translocation of chirality to the ?-position via a Cope rearrangement.

  4. Some Durability Characteristics of Micro Silica and Nano Silica Contained Concrete

    Directory of Open Access Journals (Sweden)

    Mohammed Salah Nasr

    2016-12-01

    Full Text Available This paper aims to investigate the influence of replacement of cement with nano and micro silica admixtures on some durability properties of concrete such as water absorption, chloride content and pH tests. Three replacement ratios (5%,10%,15% of micro silica and four replacement proportions (0.5%,1.5%,3%,5% for nano silica were used in this study. Two exposure conditions were considered for chloride content test: wetting-drying and full immersing exposure in 6% of chloride ions solution, NaCl type. Results showed that mixes of %5 micro silica and 5% nano silica had lower content of chloride (about 0.19% and 0.18% for wetting-drying and full immersing exposure respectively. For water absorption test, all mixes incorporated micro and nano silica, except for %5 micro silica mix, showed lower absorption than control mixes. For pH test, results indicated that the adding of nano and micro silica didn’t affect adversely the alkalinity of concrete.

  5. Alkylation of Isobutane/2-Butene Over Modified FAU-Type Zeolites.

    Science.gov (United States)

    Ro, Youngsoo; Gim, Min Yeoung; Lee, Jong Won; Lee, Eo Jin; Song, In Kyu

    2018-09-01

    A serious of mesoporous La-zeolite X catalysts (La-x-Zeol X (x = 0, 0.25, 0.5, 0.75, 1.0, and 2.0)) were prepared by a hydrothermal method with a variation of carbon template content (x, wt%). The prepared catalysts were applied to the isobutane/2-butene alkylation. Mesopore volume of the catalysts increased with increasing carbon template content, while acidity of the catalysts decreased with increasing carbon template content. In the catalytic reaction, productivity of C8 alkylate (C8 alkylate g/g-catalyst) and selectivity for C8 alkylate showed volcano-shaped trends with respect to carbon template content. Among the catalysts, La-0.5-Zeol X showed the highest productivity and selectivity for C8 alkylate. The maximum productivity and selectivity for C8 alkylate over La-0.5-Zeol X were due to the offset of two opposite trends between mesopore volume and acidity of La-x-Zeol X catalysts.

  6. Spurious cooperativity in alkylated succinic acids

    Science.gov (United States)

    Ben-Naim, A.

    1998-03-01

    The proton-proton correlation, as measured by the ratio between the second and the first dissociation constants of dibasic acid, is sometimes very large and far beyond what could be explained by electrostatic theories. We propose a novel interpretation of this phenomenon based on the idea of spurious cooperativity. The general theoretical framework underlying the onset of spurious cooperativity is developed first. The basic result is that whenever a binding (or dissociating) two-site (or more) system splits into a mixture of noninterconverting isomers the binding isotherm (or the titration curve) behaves as if it is more negatively cooperative compared with the genuine cooperativities of the individual isomer. The theory is applied to a specific system of α-α' dialkyl succinic acid. It is known that the Meso form of these alkylated derivatives show a normal correlation of the same order of magnitude as in succinic acid. On the other hand, the Racemic form of these alkylated derivatives shows anomalous strong negative correlations when the alkyl groups become large (e.g., isopropyl and tert butyl). It is shown that the theory of spurious cooperativity can explain the different behavior of the Racemic and the Meso forms, as well as the onset of anomalous strong negative correlations when the alkyl groups become large.

  7. Selective alkylation of T–T mismatched DNA using vinyldiaminotriazine–acridine conjugate

    Science.gov (United States)

    Onizuka, Kazumitsu; Usami, Akira; Yamaoki, Yudai; Kobayashi, Tomohito; Hazemi, Madoka E; Chikuni, Tomoko; Sato, Norihiro; Sasaki, Kaname; Katahira, Masato

    2018-01-01

    Abstract The alkylation of the specific higher-order nucleic acid structures is of great significance in order to control its function and gene expression. In this report, we have described the T–T mismatch selective alkylation with a vinyldiaminotriazine (VDAT)–acridine conjugate. The alkylation selectively proceeded at the N3 position of thymidine on the T–T mismatch. Interestingly, the alkylated thymidine induced base flipping of the complementary base in the duplex. In a model experiment for the alkylation of the CTG repeats DNA which causes myotonic dystrophy type 1 (DM1), the observed reaction rate for one alkylation increased in proportion to the number of T–T mismatches. In addition, we showed that primer extension reactions with DNA polymerase and transcription with RNA polymerase were stopped by the alkylation. The alkylation of the repeat DNA will efficiently work for the inhibition of replication and transcription reactions. These functions of the VDAT–acridine conjugate would be useful as a new biochemical tool for the study of CTG repeats and may provide a new strategy for the molecular therapy of DM1. PMID:29309639

  8. Isobutane alkylation over solid catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Kozorezov, Y.I.; Lisin, V.I.

    1979-05-01

    Commercial alumina modified with 6Vertical Bar3< by wt boron trifluoride was active in isobutane alkylation with ethylene in a flow reactor at 5:1 isobutane-ethylene and 5-20 min reaction time. The reaction rate was first-order in ethylene and increased with increasing temperature (20/sup 0/-80/sup 0/C) and ethylene pressure (0.2-3 atm). The calculated activation energy was 8.4 kj. Kinetic data and the activity of tert.-butyl chloride, but not ethyl chloride as alkylating agents in place of ethylene suggested a carbonium-ion chain mechanism involving both surface and gas-phase reactions. The ethylene-based yield of the alkylate decreased from 132 to 41Vertical Bar3< by wt after nine hours on stream, and its bromine number increased from 0.2 to 1 g Br/sub 2//100 ml. This inhibition was attributed to adsorption on the active acidic sites of the reaction products, particularly C/sub 10//sup +/ olefins. Catalyst stabilization could probably be achieved by selecting an appropriate solvent that would continuously desorb the inhibiting products from the catalyst surface.

  9. Microporous silica membranes

    DEFF Research Database (Denmark)

    Boffa, Vittorio; Yue, Yuanzheng

    2012-01-01

    Hydrothermal stability is a crucial factor for the application of microporous silica-based membranes in industrial processes. Indeed, it is well established that steam exposure may cause densification and defect formation in microporous silica membranes, which are detrimental to both membrane...... permeability and selectivity. Numerous previous studies show that microporous transition metal doped-silica membranes are hydrothermally more stable than pure silica membranes, but less permeable. Here we present a quantitative study on the impact of type and concentration of transition metal ions...... on the microporous structure, stability and permeability of amorphous silica-based membranes, providing information on how to design chemical compositions and synthetic paths for the fabrication of silica-based membranes with a well accessible and highly stabile microporous structure....

  10. Alkyl chitosan film-high strength, functional biomaterials.

    Science.gov (United States)

    Lu, Li; Xing, Cao; Xin, Shen; Shitao, Yu; Feng, Su; Shiwei, Liu; Fusheng, Liu; Congxia, Xie

    2017-11-01

    Biofilm with strong tensile strength is a topic item in the area of tissue engineering, medicine engineering, and so forth. Here we introduced an alkyl chitosan film with strong tensile strength and its possibility for an absorbable anticoagulation material in vivo was tested in the series of blood test, such as dynamic coagulation time, plasma recalcification time and hemolysis. Alkyl chitosan film was a better biomaterial than traditional chitosan film in the anticoagulation, tissue compatibility and cell compatibility. The unique trait of alkyl chitosan film may be for its greater contact angle and hydrophobicity ability to reduce the adsorption capacity for the blood component and the activity of fibrinolytic enzymes, enhance the antibacterial capacity than chitosan film. Moreover, none of chitosan film or butyl chitosan film exhibited quick inflammation or other disadvantage and degraded quickly by implanted test. Therefore, Alkyl chitosan film is of prospective properties as an implantable, absorbable agent for tissue heals, and this material need further research. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 3034-3041, 2017. © 2017 Wiley Periodicals, Inc.

  11. Supercritical fluid chromatography of metoprolol and analogues on aminopropyl and ethylpyridine silica without any additives.

    Science.gov (United States)

    Lundgren, Johanna; Salomonsson, John; Gyllenhaal, Olle; Johansson, Erik

    2007-06-22

    Metoprolol and a number of related amino alcohols and similar analytes have been chromatographed on aminopropyl (APS) and ethylpyridine (EPS) silica columns. The mobile phase was carbon dioxide with methanol as modifier and no amine additive was present. Optimal isocratic conditions for the selectivity were evaluated based on experiments using design of experiments. A central composite circumscribed model for each column was used. Factors were column temperature, back-pressure and % (v/v) of modifier. The responses were retention and selectivity versus metoprolol. The % of modifier mainly controlled the retention on both columns but pressure and temperature could also be important for optimizing the selectivity between the amino alcohols. The compounds could be divided into four and five groups on both columns, with respect to the selectivity. Furthermore, on the aminopropyl silica the analytes were more spread out whereas on the ethylpyridine silica, due to its aromaticity, retention and selectivity were closer. For optimal conditions the column temperature and back-pressure should be high and the modifier concentration low. A comparison of the selectivity using optimized conditions show a few switches of retention order between the two columns. On aminopropyl silica an aldehyde failed to be eluted owing to Schiff-base formation. Peak symmetry and column efficiency were briefly studied for some structurally close analogues. This revealed some activity from the columns that affected analytes that had less protected amino groups, a methyl group instead of isopropyl. The tailing was more marked with the ethylpyridine column even with the more bulky alkyl substituents. Plate number N was a better measure than the asymmetry factor since some analyte peaks broadened without serious deterioration of symmetry compared to homologues.

  12. Detection and identification of alkylating agents by using a bioinspired "chemical nose".

    Science.gov (United States)

    Hertzog-Ronen, Carmit; Borzin, Elena; Gerchikov, Yulia; Tessler, Nir; Eichen, Yoav

    2009-10-12

    Alkylating agents are simple and reactive molecules that are commonly used in many and diverse fields such as organic synthesis, medicine, and agriculture. Some highly reactive alkylating species are also being used as blister chemical-warfare agents. The detection and identification of alkylating agents is not a trivial issue because of their high reactivity and simple structure. Herein, we report on a new multispot luminescence-based approach to the detection and identification of alkylating agents. In order to demonstrate the potential of the approach, seven pi-conjugated oligomers and polymers bearing nucleophilic pyridine groups, 1-7, were adsorbed onto a solid support and exposed to vapors of alkylators 8-15. The alkylation-induced color-shift patterns of the seven-spot array allow clear discrimination of the different alkylators. The spots are sensitive to minute concentrations of alkylators and, because the detection is based on the formation of new covalent bonds, these spots saturate at about 50 ppb.

  13. Mechanisms of chemoresistance to alkylating agents in malignant glioma.

    Science.gov (United States)

    Sarkaria, Jann N; Kitange, Gaspar J; James, C David; Plummer, Ruth; Calvert, Hilary; Weller, Michael; Wick, Wolfgang

    2008-05-15

    Intrinsic or acquired chemoresistance to alkylating agents is a major cause of treatment failure in patients with malignant brain tumors. Alkylating agents, the mainstay of treatment for brain tumors, damage the DNA and induce apoptosis, but the cytotoxic activity of these agents is dependent on DNA repair pathways. For example, O6-methylguanine DNA adducts can cause double-strand breaks, but this is dependent on a functional mismatch repair pathway. Thus, tumor cell lines deficient in mismatch repair are resistant to alkylating agents. Perhaps the most important mechanism of resistance to alkylating agents is the DNA repair enzyme O6-methylguanine methyltransferase, which can eliminate the cytotoxic O6-methylguanine DNA adduct before it causes harm. Another mechanism of resistance to alkylating agents is the base excision repair (BER) pathway. Consequently, efforts are ongoing to develop effective inhibitors of BER. Poly(ADP-ribose)polymerase plays a pivotal role in BER and is an important therapeutic target. Developing effective strategies to overcome chemoresistance requires the identification of reliable preclinical models that recapitulate human disease and which can be used to facilitate drug development. This article describes the diverse mechanisms of chemoresistance operating in malignant glioma and efforts to develop reliable preclinical models and novel pharmacologic approaches to overcome resistance to alkylating agents.

  14. Alcohols as alkylating agents in heteroarene C-H functionalization

    Science.gov (United States)

    Jin, Jian; MacMillan, David W. C.

    2015-09-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of `spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  15. Alcohols as alkylating agents in heteroarene C-H functionalization.

    Science.gov (United States)

    Jin, Jian; MacMillan, David W C

    2015-09-03

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of 'spin-centre shift', during which an alcohol C-O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  16. Effect of alkyl chain length on the rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imides.

    Science.gov (United States)

    Gangamallaiah, V; Dutt, G B

    2013-10-10

    Rotational diffusion of a nonpolar solute 9-phenylanthracene (9-PA) and a cationic solute rhodamine 110 (R110) has been examined in a series of 1-alkyl-3-methylimidazolium (alkyl = octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl) bis(trifluoromethylsulfonyl)imides to understand the influence of alkyl chain length on solute rotation. In this study, reorientation times (τr) have been measured as a function of viscosity (η) by varying the temperature (T) of the solvents. These results have been analyzed using the Stokes-Einstein-Debye (SED) hydrodynamic theory along with the ones obtained for the same solutes in 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides (Gangamallaiah and Dutt, J. Phys. Chem. B 2012, 116, 12819-12825). It has been noticed that the data for 9-PA and R110 follows the relation τr = A(η/T)(n) with A being the ratio of hydrodynamic volume of the solute to the Boltzmann constant and n = 1 as envisaged by the SED theory. However, upon increasing the alkyl chain length from methyl to octadecyl significant deviations from the SED theory have been observed especially from the octyl derivative onward. From methyl to octadecyl derivatives, the value of A decreases by a factor of 3 for both the solutes and n by a factor of 1.4 and 1.6 for 9-PA and R110, respectively. These observations have been rationalized by taking into consideration the organized structure of the ionic liquids, whose influence appears to be pronounced when the number of carbon atoms in the alkyl chain attached to the imidazolium cation exceeds eight.

  17. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    Science.gov (United States)

    Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

    2015-01-01

    A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. PARP inhibitors protect against sex- and AAG-dependent alkylation-induced neural degeneration.

    Science.gov (United States)

    Allocca, Mariacarmela; Corrigan, Joshua J; Fake, Kimberly R; Calvo, Jennifer A; Samson, Leona D

    2017-09-15

    Alkylating agents are commonly used to treat cancer. Although base excision repair (BER) is a major pathway for repairing DNA alkylation damage, under certain conditions, the initiation of BER produces toxic repair intermediates that damage healthy tissues. The initiation of BER by the alkyladenine DNA glycosylase (AAG, a.k.a. MPG) can mediate alkylation-induced cytotoxicity in specific cells in the retina and cerebellum of male mice. Cytotoxicity in both wild-type and Aag -transgenic ( AagTg ) mice is abrogated in the absence of Poly(ADP-ribose) polymerase-1 (PARP1). Here, we tested whether PARP inhibitors can also prevent alkylation-induced retinal and cerebellar degeneration in male and female WT and AagTg mice. Importantly, we found that WT mice display sex-dependent alkylation-induced retinal damage (but not cerebellar damage), with WT males being more sensitive than females. Accordingly, estradiol treatment protects males against alkylation-induced retinal degeneration. In AagTg male and female mice, the alkylation-induced tissue damage in both the retina and cerebellum is exacerbated and the sex difference in the retina is abolished. PARP inhibitors, much like Parp1 gene deletion, protect against alkylation-induced AAG-dependent neuronal degeneration in WT and AagTg mice, regardless of the gender, but their efficacy in preventing alkylation-induced neuronal degeneration depends on PARP inhibitor characteristics and doses. The recent surge in the use of PARP inhibitors in combination with cancer chemotherapeutic alkylating agents might represent a powerful tool for obtaining increased therapeutic efficacy while avoiding the collateral effects of alkylating agents in healthy tissues.

  19. Crystalline Silica Primer

    Science.gov (United States)

    ,

    1992-01-01

    Crystalline silica is the scientific name for a group of minerals composed of silicon and oxygen. The term crystalline refers to the fact that the oxygen and silicon atoms are arranged in a threedimensional repeating pattern. This group of minerals has shaped human history since the beginning of civilization. From the sand used for making glass to the piezoelectric quartz crystals used in advanced communication systems, crystalline silica has been a part of our technological development. Crystalline silica's pervasiveness in our technology is matched only by its abundance in nature. It's found in samples from every geologic era and from every location around the globe. Scientists have known for decades that prolonged and excessive exposure to crystalline silica dust in mining environments can cause silicosis, a noncancerous lung disease. During the 1980's, studies were conducted that suggested that crystalline silica also was a carcinogen. As a result of these findings, crystalline silica has been regulated under the Occupational Safety and Health Administration's (OSHA) Hazard Communication Standard (HCS). Under HCS, OSHAregulated businesses that use materials containing 0.1% or more crystalline silica must follow Federal guidelines concerning hazard communication and worker training. Although the HCS does not require that samples be analyzed for crystalline silica, mineral suppliers or OSHAregulated

  20. A yeast mutant specifically sensitive to bifunctional alkylation

    International Nuclear Information System (INIS)

    Ruhland, A.; Kircher, M.; Wilborn, F.; Brendel, M.

    1981-01-01

    A mutation that specifically confers sensitivity to bi- and tri-functional alkylating agents is presented. No or little cross-sensitivity to radiation or monofunctional agents could be detected. Sensitivity does not seem to be due to preferential alkylation of mutant DNA as parent and mutant strain exhibit the same amount of DNA alkylation and the same pattern of DNA lesions including interstrand crosslinks. The mutation is due to a defect in a nuclear gene which has been designated SNM1 (sensitive to nitrogen mustard); it may control an important step in the repair of DNA interstrand crosslinks (orig.(AJ)

  1. Possible targets for the aneugenic activity of alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Pellerano, P. [IST-National Institute for Research on Cancer, Genova (Italy); Abbondandolo, A. [Univ. of Genova (Italy); Bonatti, S.; Simili, M. [CNR Institute of Mutagenesis and Differentiation, Pisa (Italy)

    1993-12-31

    Alkylating agents have been of invaluable help in mutation research for half a century. In all tested organisms, they have proved able to induce a large variety of genetic effects, including aneuploidy. Credible molecular models exist to explain the ability of alkylating agents to induce gene mutation and to act as initiators in carcinogenesis as a consequence of DNA alkylation at specific sites. On the contrary, neither the mechanism of aneuploidy induction nor the relevant cellular targets are known.

  2. Sleep-inducing N-alkyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)cinnamamides.

    Science.gov (United States)

    Houlihan, W J; Gogerty, J H; Ryan, E A; Schmitt, G

    1985-01-01

    A series of N-alkyl-3-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinones and N-alkyl-3-(trifluoromethyl)-cinnamamides were prepared and screened in a series of tests designed to detect potential sleep inducers. The more active members of the series were evaluated for their ability to induce sleep in Cebus monkeys. The most active compound, N-methyl-5-[m-(trifluoromethyl)phenyl]-5-hydroxy-2-pyrrolidinone, was equal to methaqualone.

  3. Alcohols as alkylating agents in heteroarene C–H functionalization

    Science.gov (United States)

    Jin, Jian; MacMillan, David W. C.

    2015-01-01

    Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage1. One of the core principles that underlies DNA biosynthesis is the radical-mediated elimnation of H2O to deoxygenate ribonucleotides, an example of ‘spin-center shift’ (SCS)2, during which an alcohol C–O bond is cleaved, resulting in a carbon-centered radical intermediate. While SCS is a well-understood biochemical process, it is underutilized by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylations using alcohols as radical precursors. Considering traditional radical-based alkylation methods require the use of stoichiometric oxidants, elevated temperatures, or peroxides3–7, the development of a mild protocol using simple and abundant alkylating agents would have significant utility in the synthesis of diversely functionalized pharmacophores. In this manuscript, we describe the successful execution of this idea via the development of a dual catalytic alkylation of heteroarenes using alcohols as mild alkylating reagents. This method represents the first broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer (HAT) catalysis. The utility of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone. PMID:26308895

  4. Stability studies of colloidal silica dispersions in binary solvent mixtures

    International Nuclear Information System (INIS)

    Bean, Keith Howard

    1997-01-01

    A series of monodispersed colloidal silica dispersions, of varying radii, has been prepared. These particles are hydrophilic in nature due to the presence of surface silanol groups. Some of the particles have been rendered hydrophobic by terminally grafting n-alkyl (C 18 ) chains to the surface. The stability of dispersions of these various particles has been studied in binary mixtures of liquids, namely (i) ethanol and cyclohexane, and (ii) benzene and n-heptane. The ethanol - cyclohexane systems have been studied using a variety of techniques. Adsorption excess isotherms have been established and electrophoretic mobility measurements have been made. The predicted stability of the dispersions from D.V.L.O. calculations is compared to the observed stability. The hydrophilic silica particles behave as predicted by the calculations, with the zeta potential decreasing and the van der Waals attraction increasing with increasing cyclohexane concentration. The hydrophobic particles behave differently than expected, and the stability as a function of solvent mixture composition does not show a uniform trend. The effect of varying the coverage of C 18 chains on the surface and the effect of trace water in the systems has also been investigated. Organophilic silica dispersions in benzene - n-heptane solvent mixtures show weak aggregation and phase separation into a diffuse 'gas-like' phase and a more concentrated 'liquid-like' phase, analogous to molecular condensation processes. Calculations of the van der Waals potential as a function of solvent mixture composition show good agreement with the observed stability. Determination of the number of particles in each phase at equilibrium allows the energy of flocculation to be determined using a simple thermodynamic relationship. Finally, the addition of an AB block copolymer to organophilic silica particles in benzene n-heptane solvent mixtures has been shown to have a marked effect on the dispersion stability. This stability

  5. Detection of Alkylating Agents using Electrical and Mechanical Means

    Science.gov (United States)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Tal, Shay; Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir; Eichen, Yoav

    2011-08-01

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  6. Detection of Alkylating Agents using Electrical and Mechanical Means

    International Nuclear Information System (INIS)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Eichen, Yoav; Tal, Shay; Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir

    2011-01-01

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  7. Detection of Alkylating Agents using Electrical and Mechanical Means

    Energy Technology Data Exchange (ETDEWEB)

    Gerchikov, Yulia; Borzin, Elena; Gannot, Yair; Shemesh, Ariel; Meltzman, Shai; Hertzog-Ronen, Carmit; Eichen, Yoav [Schulich Department of Chemistry, Technion-Israel Institute of Technology, Technion City, 32000, Haifa (Israel) (Israel); Tal, Shay [Present address: Systems Biology Department, Harvard Medical School, Boston, MA 02115 (United States); Stolyarova, Sara; Nemirovsky, Yael; Tessler, Nir, E-mail: chryoav@tx.technion.ac.il [Department of Electrical Engineering, Technion-Israel Institute of Technology, Technion City, 32000, Haifa (Israel)

    2011-08-17

    Alkylating agents are reactive molecules having at least one polar bond between a carbon atom and a good leaving group. These often simple molecules are frequently used in organic synthesis, as sterilizing agents in agriculture and even as anticancer agents in medicine. Unfortunately, for over a century, some of the highly reactive alkylating agents are also being used as blister chemical warfare agents. Being relatively simple to make, the risk is that these will be applied by terrorists as poor people warfare agents. The detection and identification of such alkylating agents is not a simple task because of their high reactivity and simple structure of the reactive site. Here we report on new approaches to the detection and identification of such alkylating agents using electrical (organic field effect transistors) and mechanical (microcantilevers) means.

  8. Sequence-specific DNA alkylation by tandem Py-Im polyamide conjugates.

    Science.gov (United States)

    Taylor, Rhys Dylan; Kawamoto, Yusuke; Hashiya, Kaori; Bando, Toshikazu; Sugiyama, Hiroshi

    2014-09-01

    Tandem N-methylpyrrole-N-methylimidazole (Py-Im) polyamides with good sequence-specific DNA-alkylating activities have been designed and synthesized. Three alkylating tandem Py-Im polyamides with different linkers, which each contained the same moiety for the recognition of a 10 bp DNA sequence, were evaluated for their reactivity and selectivity by DNA alkylation, using high-resolution denaturing gel electrophoresis. All three conjugates displayed high reactivities for the target sequence. In particular, polyamide 1, which contained a β-alanine linker, displayed the most-selective sequence-specific alkylation towards the target 10 bp DNA sequence. The tandem Py-Im polyamide conjugates displayed greater sequence-specific DNA alkylation than conventional hairpin Py-Im polyamide conjugates (4 and 5). For further research, the design of tandem Py-Im polyamide conjugates could play an important role in targeting specific gene sequences. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Quinone methides tethered to naphthalene diimides as selective G-quadruplex alkylating agents.

    Science.gov (United States)

    Di Antonio, Marco; Doria, Filippo; Richter, Sara N; Bertipaglia, Carolina; Mella, Mariella; Sissi, Claudia; Palumbo, Manlio; Freccero, Mauro

    2009-09-16

    We have developed novel G-quadruplex (G-4) ligand/alkylating hybrid structures, tethering the naphthalene diimide moiety to quaternary ammonium salts of Mannich bases, as quinone-methide precursors, activatable by mild thermal digestion (40 degrees C). The bis-substituted naphthalene diimides were efficiently synthesized, and their reactivity as activatable bis-alkylating agents was investigated in the presence of thiols and amines in aqueous buffered solutions. The electrophilic intermediate, quinone-methide, involved in the alkylation process was trapped, in the presence of ethyl vinyl ether, in a hetero Diels-Alder [4 + 2] cycloaddition reaction, yielding a substituted 2-ethoxychroman. The DNA recognition and alkylation properties of these new derivatives were investigated by gel electrophoresis, circular dichroism, and enzymatic assays. The alkylation process occurred preferentially on the G-4 structure in comparison to other DNA conformations. By dissecting reversible recognition and alkylation events, we found that the reversible process is a prerequisite to DNA alkylation, which in turn reinforces the G-quadruplex structural rearrangement.

  10. Noncanonical regulation of alkylation damage resistance by the OTUD4 deubiquitinase.

    Science.gov (United States)

    Zhao, Yu; Majid, Mona C; Soll, Jennifer M; Brickner, Joshua R; Dango, Sebastian; Mosammaparast, Nima

    2015-06-12

    Repair of DNA alkylation damage is critical for genomic stability and involves multiple conserved enzymatic pathways. Alkylation damage resistance, which is critical in cancer chemotherapy, depends on the overexpression of alkylation repair proteins. However, the mechanisms responsible for this upregulation are unknown. Here, we show that an OTU domain deubiquitinase, OTUD4, is a positive regulator of ALKBH2 and ALKBH3, two DNA demethylases critical for alkylation repair. Remarkably, we find that OTUD4 catalytic activity is completely dispensable for this function. Rather, OTUD4 is a scaffold for USP7 and USP9X, two deubiquitinases that act directly on the AlkB proteins. Moreover, we show that loss of OTUD4, USP7, or USP9X in tumor cells makes them significantly more sensitive to alkylating agents. Taken together, this work reveals a novel, noncanonical mechanism by which an OTU family deubiquitinase regulates its substrates, and provides multiple new targets for alkylation chemotherapy sensitization of tumors. © 2015 The Authors.

  11. Orientational diffusion of n-alkyl cyanides

    International Nuclear Information System (INIS)

    Zhu Xiang; Farrer, Richard A; Zhong Qin; Fourkas, John T

    2005-01-01

    Ultrafast optical Kerr effect spectroscopy has been used to study the temperature-dependent orientational dynamics of a series of nitriles with n-alkyl chains ranging from one to 11 carbons in length. In all cases the orientational diffusion is found to be described by a single-exponential decay. Analysis of the orientational correlation times using the Debye-Stokes-Einstein equation suggests that the molecules adopt extended configurations and reorient as rigid rods. The liquids with shorter alkyl chains undergo an apparent ordering transition as they are cooled

  12. Mechanisms of resistance to alkylating agents

    OpenAIRE

    Damia, G.; D‘Incalci, M.

    1998-01-01

    Alkylating agents are the most widely used anticancer drugs whose main target is the DNA, although how exactly the DNA lesions cause cell death is still not clear. The emergence of resistance to this class of drugs as well as to other antitumor agents is one of the major causes of failure of cancer treatment. This paper reviews some of the best characterized mechanisms of resistance to alkylating agents. Pre- and post-target mechanisms are recognized, the former able to limit the formation of...

  13. Radiation-chemical alkylation of olefines with adamantane

    International Nuclear Information System (INIS)

    Podkhalyuzin, A.T.; Vikulin, V.V.; Morozov, V.A.; Nazarova, M.P.; Vereshchinskii, I.V.

    1977-01-01

    Radiation-chemical alkylation of C 2 to C 4 olefines with adamantane was studied in gas phase at temperatures 270 to 430 0 C. The main reaction product is monoalkyladamantane. The reaction proceeds by a free radical chain mechanism. The effective activation energy is of the order of 8 to 10 kcal/mole. Thermal alkylation was carried out for comparison and the contribution of the thermal component to the radiation-thermal process was estimated. Liquid phase alkylation of hexafluoropropylene with adamantane was studied in the presence of solvents. Under various conditions mono- and di-substituted adamantanes are produced containing fluorine in end groups. These compounds were converted to corresponding fluoroalkenyladamantanes by dehydrofluorination. The kinetic parameters were calculated and physical-chemical data concerning some of the resulting products were determined. (author)

  14. Preparation and evaluation of poly(alkyl methacrylate-co-methacrylic acid-co-ethylene dimethacrylate) monolithic columns for separating polar small molecules by capillary liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Shu-Ling; Wu, Yu-Ru; Lin, Tzuen-Yeuan; Fuh, Ming-Ren, E-mail: msfuh@scu.edu.tw

    2015-04-29

    Highlights: • Methacrylic acid (MAA) was used to increase hydrophilicity of polymeric monoliths. • Fast separation of phenol derivatives was achieved in 5 min using MAA-incorporated column. • Separations of aflatoxins and phenicol antibiotics were achieved using MAA-incorporated column. - Abstract: In this study, methacrylic acid (MAA) was incorporated with alkyl methacrylates to increase the hydrophilicity of the synthesized ethylene dimethacrylate-based (EDMA-based) monoliths for separating polar small molecules by capillary LC analysis. Different alkyl methacrylate–MAA ratios were investigated to prepare a series of 30% alkyl methacrylate–MAA–EDMA monoliths in fused-silica capillaries (250-μm i.d.). The porosity, permeability, and column efficiency of the synthesized MAA-incorporated monolithic columns were characterized. A mixture of phenol derivatives is employed to evaluate the applicability of using the prepared monolithic columns for separating small molecules. Fast separation of six phenol derivatives was achieved in 5 min with gradient elution using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. In addition, the effect of acetonitrile content in mobile phase on retention factor and plate height as well as the plate height-flow velocity curves were also investigated to further examine the performance of the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. Moreover, the applicability of prepared polymer-based monolithic column for potential food safety applications was also demonstrated by analyzing five aflatoxins and three phenicol antibiotics using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column.

  15. Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

    Science.gov (United States)

    Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-07-27

    A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics.

    Science.gov (United States)

    Anderson, Eric; Crisci, Anthony; Murugappan, Karthick; Román-Leshkov, Yuriy

    2017-05-22

    Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO 2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H 3 PMo 12 O 40 /TiO 2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 40 CFR 721.5985 - Fatty alkyl phosphate, alkali metal salt (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty alkyl phosphate, alkali metal... Specific Chemical Substances § 721.5985 Fatty alkyl phosphate, alkali metal salt (generic). (a) Chemical... as a fatty alkyl phosphate, alkali metal salt (PMN P-99-0385) is subject to reporting under this...

  18. An adaptive response to alkylating agents in Aspergillus nidulans.

    Science.gov (United States)

    Hooley, P; Shawcross, S G; Strike, P

    1988-11-01

    A simple method is described for demonstrating adaptation to alkylation damage in Aspergillus nidulans. One wild type, two MNNG-sensitive, and one MNNG-resistant strain all showed improvement in colony growth when challenged with MNNG following appropriate inducing pretreatments. Other alkylating agents (MMS, EMS) could also adapt mycelium to later MNNG challenge, while 4NQO and UV could not. The inducible effect was not transmissible through conidia. A standard reversion assay based upon methG proved impractical for studying mutation frequencies during alkylation treatments owing to variations in MNNG resistance amongst revertants.

  19. 40 CFR 721.520 - Alanine, N-(2-carboxyethyl)-N-alkyl-, salt.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alanine, N-(2-carboxyethyl)-N-alkyl... Specific Chemical Substances § 721.520 Alanine, N-(2-carboxyethyl)-N-alkyl-, salt. (a) Chemical substance... alanine, N-(2-carboxyethyl)-N- alkyl-, salt (P-89-336) is subject to reporting under this section for the...

  20. Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane

    Energy Technology Data Exchange (ETDEWEB)

    Daniel M. Ginosar; David N. Ghompson; Kyle C. Burch

    2005-01-01

    Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical isobutane. A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical isobutane over the catalyst bed at different reactivation conditions. Temperature, pressure and regeneration time were found to play important roles in the supercritical isobutane regeneration process when applied to a completely deactivated USY zeolite alkylation catalyst. Manipulation of the variables that influence solvent strength, diffusivity, surface desorption, hydride transfer rates, and coke aging, strongly influence regeneration effectiveness.

  1. Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts

    DEFF Research Database (Denmark)

    Khokarale, Santosh Govind; He, Jian; Schill, Leonhard

    2018-01-01

    Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO2 in methanol at 220 °C and 50 bar H2 . A synergistic effect of Ni increased the yield of MP...... of the material. Interestingly, it was observed that Fe-Ni/ZrO2 also effectively catalyzed methanol reforming to produce H2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N2 instead of H2. Fe-Ni/ZrO2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl...

  2. 4-Alkyl radical extrusion in the cytochrome P-450-catalyzed oxidation of 4-alkyl-1,4-dihydropyridines

    International Nuclear Information System (INIS)

    Lee, J.S.; Jacobsen, N.E.; Ortiz de Montellano, P.R.

    1988-01-01

    Rat liver microsomal cytochrome P-450 oxidizes the 4-methyl, 4-ethyl (DDEP), and 4-isopropyl derivatives of 3,5-bis(carbethoxy)-2,6-dimethyl-1,4,-dihydropyridine to mixtures of the corresponding 4-alkyl and 4-dealkyl pyridines. A fraction of the total microsomal enzyme is destroyed in the process. The 4-dealkyl to 4-alkyl pyridine metabolite ratio, the extent of cytochrome P-450 destruction, and the rate of spin-trapped radical accumulation are correlated in a linear inverse manner with the homolytic or heterolytic bond energies of the 4-alkyl groups of the 4-alkyl-1,4-dihydropyridines. No isotope effects are observed on the pyridine matabolite ratio, the destruction of cytochrome P-450, or the formation of ethyl radicals when [4- 2 H]DDEP is used instead of DDEP. N-Methyl- and N-ethyl-DDEP undergo N-dealkylation rather than aromatization but N-phenyl-DDEP is oxidized to a mixture of the 4-ethyl and 4-deethyl N-phenylpyridinium metabolites. In contrast to the absence of an isotope effect in the oxidation of DDEP, the 4-deethyl to 4-ethyl N-phenylpyridinium metabolite ratio increases 6-fold when N-phenyl[4- 2 H]DDEP is used. The results support the hypothesis that cytochrome P-450 catalyzes the oxidation of dihydropyridines to radical cations and show that the radical cations decay to nonradical products by multiple, substituent-dependent, mechanisms

  3. Final Technical Report [Development of Catalytic Alkylation and Fluoroalkylation Methods

    Energy Technology Data Exchange (ETDEWEB)

    Vicic, David A.

    2014-05-01

    In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands. We found that reaction of (TMEDA)NiMe2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy’)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr{sub 2}] and [Ni(COD){sub 2}] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72 % isolated) by the precipitation of 1 from THF solvent.

  4. Alkylation of hydrothiophosphoryl compounds in conditions of interphase catalysis

    International Nuclear Information System (INIS)

    Aladzheva, I.M.; Odinets, I.L.; Petrovskij, P.V.; Mastryukova, T.A.; Kabachkin, M.I.

    1993-01-01

    A method of interphase catalysis permitted to develop a common method for synthesis of compounds with thiophosphoryl group. The effect of nature of hydrothiophosphoryl compound, alkylating agent, two-phase system and reaction conditions on alkylation product yields was investigated in detail

  5. Direct, Regioselective N-Alkylation of 1,3-Azoles.

    Science.gov (United States)

    Chen, Shuai; Graceffa, Russell F; Boezio, Alessandro A

    2016-01-04

    Regioselective N-alkylation of 1,3-azoles is a valuable transformation. Organomagnesium reagents were discovered to be competent bases to affect regioselective alkylation of various 1,3-azoles. Counterintuitively, substitution selectively occurred at the more sterically hindered nitrogen atom. Numerous examples are provided, on varying 1,3-azole scaffolds, with yields ranging from 25 to 95%.

  6. Propargyl organometallic compounds. II. Alkylation of sodium derivatives of 1-alkyl-1-aryl-2-alkynes in liquid ammonia

    International Nuclear Information System (INIS)

    Libman, N.M.; Sevryukov, Yu.P.

    1987-01-01

    In most cases the alkylation of the sodium derivatives of 1-phenyl-1-alkyl-2-alkynes by methyl, ethyl, isopropyl, and tert-butyl bromides in liquid ammonia takes place preferentially at the sp 2 -hybridized carbon atom, and this leads to the formation of the corresponding acetylenes, The regioselectivity of the reaction is explained by the greater softness of the trigonal atom of the ambient propargyl anion and its smaller screening by the solvate shell compared with the diagonal atom

  7. Strategy for the extraction of yeast DNA from artisan agave must for quantitative PCR analysis.

    Science.gov (United States)

    Kirchmayr, Manuel Reinhart; Segura-Garcia, Luis Eduardo; Flores-Berrios, Ericka Patricia; Gschaedler, Anne

    2011-11-01

    An efficient method for the direct extraction of yeast genomic DNA from agave must was developed. The optimized protocol, which was based on silica-adsorption of DNA on microcolumns, included an enzymatic cell wall degradation step followed by prolonged lysis with hot detergent. The resulting extracts were suitable templates for subsequent qPCR assays that quantified mixed yeast populations in artisan Mexican mezcal fermentations. Copyright © 2011 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  8. Alkylation sensitivity screens reveal a conserved cross-species functionome

    Science.gov (United States)

    Svilar, David; Dyavaiah, Madhu; Brown, Ashley R.; Tang, Jiang-bo; Li, Jianfeng; McDonald, Peter R.; Shun, Tong Ying; Braganza, Andrea; Wang, Xiao-hong; Maniar, Salony; St Croix, Claudette M.; Lazo, John S.; Pollack, Ian F.; Begley, Thomas J.; Sobol, Robert W.

    2013-01-01

    To identify genes that contribute to chemotherapy resistance in glioblastoma, we conducted a synthetic lethal screen in a chemotherapy-resistant glioblastoma derived cell line with the clinical alkylator temozolomide (TMZ) and an siRNA library tailored towards “druggable” targets. Select DNA repair genes in the screen were validated independently, confirming the DNA glycosylases UNG and MYH as well as MPG to be involved in the response to high dose TMZ. The involvement of UNG and MYH is likely the result of a TMZ-induced burst of reactive oxygen species. We then compared the human TMZ sensitizing genes identified in our screen with those previously identified from alkylator screens conducted in E. coli and S. cerevisiae. The conserved biological processes across all three species composes an Alkylation Functionome that includes many novel proteins not previously thought to impact alkylator resistance. This high-throughput screen, validation and cross-species analysis was then followed by a mechanistic analysis of two essential nodes: base excision repair (BER) DNA glycosylases (UNG, human and mag1, S. cerevisiae) and protein modification systems, including UBE3B and ICMT in human cells or pby1, lip22, stp22 and aim22 in S. cerevisiae. The conserved processes of BER and protein modification were dual targeted and yielded additive sensitization to alkylators in S. cerevisiae. In contrast, dual targeting of BER and protein modification genes in human cells did not increase sensitivity, suggesting an epistatic relationship. Importantly, these studies provide potential new targets to overcome alkylating agent resistance. PMID:23038810

  9. Alkylation damage in DNA and RNA--repair mechanisms and medical significance

    DEFF Research Database (Denmark)

    Drabløs, Finn; Feyzi, Emadoldin; Aas, Per Arne

    2004-01-01

    Alkylation lesions in DNA and RNA result from endogenous compounds, environmental agents and alkylating drugs. Simple methylating agents, e.g. methylnitrosourea, tobacco-specific nitrosamines and drugs like temozolomide or streptozotocin, form adducts at N- and O-atoms in DNA bases. These lesions...... are mainly repaired by direct base repair, base excision repair, and to some extent by nucleotide excision repair (NER). The identified carcinogenicity of O(6)-methylguanine (O(6)-meG) is largely caused by its miscoding properties. Mutations from this lesion are prevented by O(6)-alkylG-DNA alkyltransferase......, inactivation of the MMR system in an AGT-defective background causes resistance to the killing effects of O(6)-alkylating agents, but not to the mutagenic effect. Bifunctional alkylating agents, such as chlorambucil or carmustine (BCNU), are commonly used anti-cancer drugs. DNA lesions caused by these agents...

  10. A new strategy for aromatic ring alkylation in cylindrocyclophane biosynthesis.

    Science.gov (United States)

    Nakamura, Hitomi; Schultz, Erica E; Balskus, Emily P

    2017-08-01

    Alkylation of aromatic rings with alkyl halides is an important transformation in organic synthesis, yet an enzymatic equivalent is unknown. Here, we report that cylindrocyclophane biosynthesis in Cylindrospermum licheniforme ATCC 29412 involves chlorination of an unactivated carbon center by a novel halogenase, followed by a previously uncharacterized enzymatic dimerization reaction featuring sequential, stereospecific alkylations of resorcinol aromatic rings. Discovery of the enzymatic machinery underlying this unique biosynthetic carbon-carbon bond formation has implications for biocatalysis and metabolic engineering.

  11. 40 CFR 721.2565 - Alkylated sulfonated diphenyl oxide, alkali and amine salts.

    Science.gov (United States)

    2010-07-01

    ..., alkali and amine salts. 721.2565 Section 721.2565 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.2565 Alkylated sulfonated diphenyl oxide, alkali and... substances identified as alkylated sulfonated diphenyl oxide, alkali salt (PMN P-93-352) and alkylated...

  12. Comparative study of oxidative stress caused by anthracene and alkyl-anthracenes in

    Directory of Open Access Journals (Sweden)

    Ji-Yeon Roh

    2018-02-01

    Full Text Available Oxidative stress was evaluated for anthracene (Ant and alkyl-Ants (9-methylanthracene [9-MA] and 9,10-dimethylanthracene [9,10-DMA] in Caenorhabditis elegans to compare changes in toxicity due to the degree of alkylation. Worms were exposed at 1 the same external exposure concentration and 2 the maximum water-soluble concentration. Formation of reactive oxygen species, superoxide dismutase activity, total glutathione concentration, and lipid peroxidation were determined under constant exposure conditions using passive dosing. The expression of oxidative stress-related genes (daf-2, sir-2.1, daf-16, sod-1, sod-2, sod-3 and cytochrome 35A/C family genes was also investigated to identify and compare changes in the genetic responses of C. elegans exposed to Ant and alkyl-Ant. At the same external concentration, 9,10-DMA induced the greatest oxidative stress, as evidenced by all indicators, except for lipid peroxidation, followed by 9-MA and Ant. Interestingly, 9,10-DMA led to greater oxidative stress than 9-MA and Ant when worms were exposed to the maximum water-soluble concentration, although the maximum water-soluble concentration of 9,10-DMA is the lowest. Increased oxidative stress by alkyl-Ants would be attributed to higher lipid-water partition coefficient and the π electron density in aromatic rings by alkyl substitution, although this supposition requires further confirmation.

  13. Optimization of the alkyl side chain length of fluorine-18-labeled 7α-alkyl-fluoroestradiol

    International Nuclear Information System (INIS)

    Okamoto, Mayumi; Shibayama, Hiromitsu; Naka, Kyosuke; Kitagawa, Yuya; Ishiwata, Kiichi; Shimizu, Isao; Toyohara, Jun

    2016-01-01

    Introduction: Several lines of evidence suggest that 7α-substituted estradiol derivatives bind to the estrogen receptor (ER). In line with this hypothesis, we designed and synthesized 18 F-labeled 7α-fluoroalkylestradiol (Cn-7α-[ 18 F]FES) derivatives as molecular probes for visualizing ERs. Previously, we successfully synthesized 7α-(3-[ 18 F]fluoropropyl)estradiol (C3-7α-[ 18 F]FES) and showed promising results for quantification of ER density in vivo, although extensive metabolism was observed in rodents. Therefore, optimization of the alkyl side chain length is needed to obtain suitable radioligands based on Cn-7α-substituted estradiol pharmacophores. Methods: We synthesized fluoromethyl (23; C1-7α-[ 18 F]FES) to fluorohexyl (26; C6-7α-[ 18 F]FES) derivatives, except fluoropropyl (C3-7α-[ 18 F]FES) and fluoropentyl derivatives (C5-7α-[ 18 F]FES), which have been previously synthesized. In vitro binding to the α-subtype (ERα) isoform of ERs and in vivo biodistribution studies in mature female mice were carried out. Results: The in vitro IC 50 value of Cn-7α-FES tended to gradually decrease depending on the alkyl side chain length. C1-7α-[ 18 F]FES (23) showed the highest uptake in ER-rich tissues such as the uterus. Uterus uptake also gradually decreased depending on the alkyl side chain length. As a result, in vivo uterus uptake reflected the in vitro ERα affinity of each compound. Bone uptake, which indicates de-fluorination, was marked in 7α-(2-[ 18 F]fluoroethyl)estradiol (C2-7α-[ 18 F]FES) (24) and 7α-(4-[ 18 F]fluorobutyl)estradiol (C4-7α-[ 18 F]FES) (25) derivatives. However, C1-7α-[ 18 F]FES (23) and C6-7α-[ 18 F]FES (26) showed limited uptake in bone. As a result, in vivo bone uptake (de-fluorination) showed a bell-shaped pattern, depending on the alkyl side chain length. C1-7α-[ 18 F]FES (23) showed the same levels of uptake in uterus and bone compared with those of 16α-[ 18 F]fluoro-17β-estradiol. Conclusions: The optimal alkyl

  14. Selective sp3 C-H alkylation via polarity-match-based cross-coupling.

    Science.gov (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W; Li, Ximing; MacMillan, David W C

    2017-07-06

    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp 3 )-C(sp 2 ) coupling, there is a growing demand for C-H alkylation reactions, wherein sp 3 C-H bonds are replaced with sp 3 C-alkyl groups. Here we describe a polarity-match-based selective sp 3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp 3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  15. Aag DNA glycosylase promotes alkylation-induced tissue damage mediated by Parp1.

    Science.gov (United States)

    Calvo, Jennifer A; Moroski-Erkul, Catherine A; Lake, Annabelle; Eichinger, Lindsey W; Shah, Dharini; Jhun, Iny; Limsirichai, Prajit; Bronson, Roderick T; Christiani, David C; Meira, Lisiane B; Samson, Leona D

    2013-04-01

    Alkylating agents comprise a major class of front-line cancer chemotherapeutic compounds, and while these agents effectively kill tumor cells, they also damage healthy tissues. Although base excision repair (BER) is essential in repairing DNA alkylation damage, under certain conditions, initiation of BER can be detrimental. Here we illustrate that the alkyladenine DNA glycosylase (AAG) mediates alkylation-induced tissue damage and whole-animal lethality following exposure to alkylating agents. Aag-dependent tissue damage, as observed in cerebellar granule cells, splenocytes, thymocytes, bone marrow cells, pancreatic β-cells, and retinal photoreceptor cells, was detected in wild-type mice, exacerbated in Aag transgenic mice, and completely suppressed in Aag⁻/⁻ mice. Additional genetic experiments dissected the effects of modulating both BER and Parp1 on alkylation sensitivity in mice and determined that Aag acts upstream of Parp1 in alkylation-induced tissue damage; in fact, cytotoxicity in WT and Aag transgenic mice was abrogated in the absence of Parp1. These results provide in vivo evidence that Aag-initiated BER may play a critical role in determining the side-effects of alkylating agent chemotherapies and that Parp1 plays a crucial role in Aag-mediated tissue damage.

  16. Aag DNA glycosylase promotes alkylation-induced tissue damage mediated by Parp1.

    Directory of Open Access Journals (Sweden)

    Jennifer A Calvo

    2013-04-01

    Full Text Available Alkylating agents comprise a major class of front-line cancer chemotherapeutic compounds, and while these agents effectively kill tumor cells, they also damage healthy tissues. Although base excision repair (BER is essential in repairing DNA alkylation damage, under certain conditions, initiation of BER can be detrimental. Here we illustrate that the alkyladenine DNA glycosylase (AAG mediates alkylation-induced tissue damage and whole-animal lethality following exposure to alkylating agents. Aag-dependent tissue damage, as observed in cerebellar granule cells, splenocytes, thymocytes, bone marrow cells, pancreatic β-cells, and retinal photoreceptor cells, was detected in wild-type mice, exacerbated in Aag transgenic mice, and completely suppressed in Aag⁻/⁻ mice. Additional genetic experiments dissected the effects of modulating both BER and Parp1 on alkylation sensitivity in mice and determined that Aag acts upstream of Parp1 in alkylation-induced tissue damage; in fact, cytotoxicity in WT and Aag transgenic mice was abrogated in the absence of Parp1. These results provide in vivo evidence that Aag-initiated BER may play a critical role in determining the side-effects of alkylating agent chemotherapies and that Parp1 plays a crucial role in Aag-mediated tissue damage.

  17. Selective sp3 C-H alkylation via polarity-match-based cross-coupling

    Science.gov (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

    2017-07-01

    The functionalization of carbon-hydrogen (C-H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence. Although many C-H functionalization reactions involve C(sp3)-C(sp2) coupling, there is a growing demand for C-H alkylation reactions, wherein sp3 C-H bonds are replaced with sp3 C-alkyl groups. Here we describe a polarity-match-based selective sp3 C-H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C-H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl-alkyl fragment coupling. The sp3 C-H alkylation is highly selective for the α-C-H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry.

  18. Microcolumn-based speciation analysis of thallium in soil and green cabbage.

    Science.gov (United States)

    Jia, Yanlong; Xiao, Tangfu; Sun, Jialong; Yang, Fei; Baveye, Philippe C

    2018-07-15

    Thallium (Tl) is a toxic trace metal, whose geochemical behavior and biological effects are closely controlled by its chemical speciation in the environment. However, little tends to be known about this speciation of Tl in soil and plant systems that directly affect the safety of food supplies. In this context, the objective of the present study was to elaborate an efficient method to separate and detect Tl(I) and Tl(III) species for soil and plant samples. This method involves the selective adsorption of Tl(I) on microcolumns filled with immobilized oxine, in the presence of DTPA (diethylenetriaminepentaacetic acid), followed by DTPA-enhanced ultrasonic and heating-induced extraction, coupled with ICP-MS detection. The method was characterized by a LOD of 0.037 μg/L for Tl(I) and 0.18 μg/L for Tl(III) in 10  mL samples. With this method, a second objective of the research was to assess the speciation of Tl in pot and field soils and in green cabbage crops. Experimental results suggest that DTPA extracted Tl was mainly present as Tl(I) in soils (>95%). Tl in hyperaccumulator plant green cabbage was also mainly present as Tl(I) (>90%). With respect to Tl uptake in plants, this study provides direct evidence that green cabbage mainly takes up Tl(I) from soil, and transports it into the aboveground organs. In soils, Tl(III) is reduced to Tl(I) even at the surface where the chemical environment promotes oxidation. This observation is conducive to understanding the mechanisms of Tl isotope fractionation in the soil-plant system. Based on geochemical fraction studies, the reducible fraction was the main source of Tl getting accumulated by plants. These results indicate that the improved analytical method presented in this study offers an economical, simple, fast, and sensitive approach for the separation of Tl species present in soils at trace levels. Copyright © 2018 Elsevier B.V. All rights reserved.

  19. Silica-Immobilized Enzyme Reactors

    Science.gov (United States)

    2007-08-01

    Silica-IMERs 14 implicated in neurological disorders such as Schizophrenia and Parkinson’s disease.[86] Drug discovery for targets that can alter the...primarily the activation of prodrugs and proantibiotics for cancer treatments or antibiotic therapy , respectively.[87] Nitrobenzene nitroreductase was...BuChE) Monolith disks* Packed Silica Biosilica Epoxide- Silica Silica-gel Enzyme Human AChE Human AChE Human AChE Equine BuChE Human

  20. MASS BALANCE OF SILICA IN STRAW FROM THE PERSPECTIVE OF SILICA REDUCTION IN STRAW PULP

    Directory of Open Access Journals (Sweden)

    Celil Atik,

    2012-06-01

    Full Text Available The high silica content of wheat straw is an important limiting factor for straw pulping. High silica content complicates processing and black liquor recovery, wears out factory installations, and lowers paper quality. Each section of wheat straw has different cells and chemical compositions and thus different silica content. In this work, the silica content of balled straw samples were examined according to their physical components, including internodes, nodes, leaves (sheath and blade, rachis, grain, other plant bodies, and other plant spikes. Mass distribution of silica was determined by a dry ashing method. Half (50.90% of the silica comes from leaves, and its mechanical separation will reduce the silica content in wheat straw pulp significantly. Destroying silica bodies by sonication will increase the strength properties of straw pulp.

  1. Regulation of DNA Alkylation Damage Repair: Lessons and Therapeutic Opportunities.

    Science.gov (United States)

    Soll, Jennifer M; Sobol, Robert W; Mosammaparast, Nima

    2017-03-01

    Alkylation chemotherapy is one of the most widely used systemic therapies for cancer. While somewhat effective, clinical responses and toxicities of these agents are highly variable. A major contributing factor for this variability is the numerous distinct lesions that are created upon alkylation damage. These adducts activate multiple repair pathways. There is mounting evidence that the individual pathways function cooperatively, suggesting that coordinated regulation of alkylation repair is critical to prevent toxicity. Furthermore, some alkylating agents produce adducts that overlap with newly discovered methylation marks, making it difficult to distinguish between bona fide damaged bases and so-called 'epigenetic' adducts. Here, we discuss new efforts aimed at deciphering the mechanisms that regulate these repair pathways, emphasizing their implications for cancer chemotherapy. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Liquid Phase Deposition of Silica on the Hexagonally Close-Packed Monolayer of Silica Spheres

    Directory of Open Access Journals (Sweden)

    Seo Young Yoon

    2013-01-01

    Full Text Available Liquid phase deposition is a method used for the nonelectrochemical production of polycrystalline ceramic films at low temperatures, most commonly silicon dioxide films. Herein, we report that silica spheres are organized in a hexagonal close-packed array using a patterned substrate. On this monolayer of silica spheres, we could fabricate new nanostructures in which deposition and etching compete through a modified LPD reaction. In the early stage, silica spheres began to undergo etching, and then, silica bridges between the silica spheres appeared by the local deposition reaction. Finally, the silica spheres and bridges disappeared completely. We propose the mechanism for the formation of nanostructure.

  3. Synthesis and Biological Evaluation of N-Alkyl-3-(alkylamino-pyrazine-2-carboxamides

    Directory of Open Access Journals (Sweden)

    Lucia Semelkova

    2015-05-01

    Full Text Available A series of N-alkyl-3-(alkylaminopyrazine-2-carboxamides and their N-alkyl-3-chloropyrazine-2-carboxamide precursors were prepared. All compounds were characterized by analytical methods and tested for antimicrobial and antiviral activity. The antimycobacterial MIC values against Mycobacterium tuberculosis H37Rv of the most effective compounds, 3-(hexylamino-, 3-(heptylamino- and 3-(octylamino-N-methyl-pyrazine-2-carboxamides 14‒16, was 25 μg/mL. The compounds inhibited photosystem 2 photosynthetic electron transport (PET in spinach chloroplasts. This activity was strongly connected with the lipophilicity of the compounds. For effective PET inhibition longer alkyl chains in the 3-(alkylamino substituent in the N-alkyl-3-(alkylaminopyrazine-2-carboxamide molecule were more favourable than two shorter alkyl chains.

  4. Synthesis of trideuterated O-alkyl platelet activating factor and lyso derivatives

    International Nuclear Information System (INIS)

    Prakash, C.; Saleh, S.; Taber, D.F.; Blair, I.A.

    1989-01-01

    Racemic heavy isotope analogs of 1-O-alkyl-sn-glycero-3-phosphocholine (lysoPAF) and 1-O-alkyl-2-O-acetyl-sn-glycero-3-phosphocholine (PAF) were prepared for use as internal standards to facilitate quantitative studies based on mass spectrometry. Starting from pentadecane-1,15-diol and rac-glycerol-1,2-acetonide, a convergent synthesis of 1-O-[16'-2H3]hexadecyl and 1-O-[18'-2H3]octadecyl rac-glycero-3-phosphocholine and their acetyl derivatives is described. Three deuterium atoms were introduced at the terminal position of the 1-O-alkyl group by displacement of the p-toluensulfonyl group from 1-O-alkyl-15'-p-toluensulfonate and 1-O-alkyl-17'-p-toluensulfonate with [2H3]-methylmagnesium iodide. The 1-O-alkyl-17'-p-toluensulfonate was obtained by reaction of the 1-O-alkyl-15'-p-toluensulfonate with allylmagnesium bromide, followed by reductive ozonolysis and treatment with p-toluene-sulfonyl chloride. The hydroxyl group at C-2 was protected by a benzyl group and removed at a late stage in the synthesis. This provided the corresponding lyso-derivatives or allowed preparation of racemic PAF by subsequent acetylation of the free hydroxy group. The phosphocholine moiety was introduced at glycerol C-3 by reaction with bromoethyldichlorophosphate and trimethylamine. The synthetic compounds were analyzed by FAB/MS and GC/NICIMS. They were shown to contain less than 0.6% protium impurity

  5. The Impact of Commonly Used Alkylating Agents on Artifactual Peptide Modification.

    Science.gov (United States)

    Hains, Peter G; Robinson, Phillip J

    2017-09-01

    Iodoacetamide is by far the most commonly used agent for alkylation of cysteine during sample preparation for proteomics. An alternative, 2-chloroacetamide, has recently been suggested to reduce the alkylation of residues other than cysteine, such as the N-terminus, Asp, Glu, Lys, Ser, Thr, and Tyr. Here we show that although 2-chloroacetamide reduces the level of off-target alkylation, it exhibits a range of adverse effects. The most significant of these is methionine oxidation, which increases to a maximum of 40% of all Met-containing peptides, compared with 2-5% with iodoacetamide. Increases were also observed for mono- and dioxidized tryptophan. No additional differences between the alkylating reagents were observed for a range of other post-translational modifications and digestion parameters. The deleterious effects were observed for 2-chloroacetamide from three separate suppliers. The adverse impact of 2-chloroacetamide on methionine oxidation suggests that it is not the ideal alkylating reagent for proteomics.

  6. Balancing repair and tolerance of DNA damage caused by alkylating agents

    OpenAIRE

    Fu, Dragony; Calvo, Jennifer A.; Samson, Leona D.

    2012-01-01

    Alkylating agents constitute a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER) and mismatch repair (MMR), respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial ...

  7. γ-radiolysis of dialkyl, alkyl-aryl and diaryl sulphones

    International Nuclear Information System (INIS)

    Bowmer, T.N.; O'Donnell, J.H.

    1981-01-01

    Dialkyl sulphones, RSO 2 R, have been considered as model compounds for the radiolysis of poly(olefin sulphone)s. They show preferential C-S scission and SO 2 elimination, attributable to the relatively low strengths of these bonds. Combination of the alkyl radicals, which are produced singly or in pairs according to whether one or two C-S scissions occur in one molecule, competes with hydrogen abstraction from sulphone molecules. The latter is favoured for single C-S scissions and as the size of the radical increases and hence its mobility decreases. An important degradation reaction in radiolysis is considered to be ionization to form the cation radical of the dialkyl sulphone, followed by a single C-S scission to produce the alkyl radical and the complementary alkyl sulphonyl cation, which may undergo scission of the remaining C-S bond to produce SO 2 . GC/MS studies of the volatile products from dimethyl sulphone have shown that radiolysis results in a complexity of fragmentation and combination reactions, involving scission of most bonds in the molecule. The variety of products has been confirmed using CD 3 SO 2 CD 3 . Radiation protection by aromatic substituents has been demonstrated and branched alkyls have been shown to give higher yields of alkanes and SO 2 than linear alkyls. (author)

  8. Complex responses to alkylating agents

    International Nuclear Information System (INIS)

    Samson, L.D.

    2003-01-01

    Using Affymetrix oligonucleotide GeneChip analysis, we previously found that, upon exposure to the simple alkylating agent methylmethane sulfonate, the transcript levels for about one third of the Saccharomyces cerevisiae genome (∼2,000 transcripts) are induced or repressed during the first hour or two after exposure. In order to determine whether the responsiveness of these genes has any relevance to the protection of cells against alkylating agents we have undertaken several follow-up studies. First, we explored the specificity of this global transcriptional response to MMS by measuring the global response of S. cerevisiae to a broad range of agents that are known to induce DNA damage. We found that each agent produced a very different mRNA transcript profile, even though the exposure doses produced similar levels of toxicity. We also found that the selection of genes that respond to MMS is highly dependent upon what cell cycle phase the cells are in at the time of exposure. Computational clustering analysis of the dataset derived from a large number of exposures identified several promoter motifs that are likely to control some of the regulons that comprise this large set of genes that are responsive to DNA damaging agents. However, it should be noted that these agents damage cellular components other than DNA, and that the responsiveness of each gene need not be in response to DNA damage per se. We have also begun to study the response of other organisms to alkylating agents, and these include E. coli, cultured mouse and human cells, and mice. Finally, we have developed a high throughput phenotypic screening method to interrogate the role of all non-essential S. cerevisiae genes (about 4,800) in protecting S. cerevisiae against the deleterious effects of alkylating agents; we have termed this analysis 'genomic phenotyping'. This study has uncovered a plethora of new pathways that play a role in the recovery of eukaryotic cells after exposure to toxic

  9. Grafting of polymer onto silica surface in the presence of γ-ray irradiated silica

    International Nuclear Information System (INIS)

    Tsuchida, A.; Yokoyama, R.; Takami, M.; Chen, J.; Ohta, M.; Tsubokawa, N.

    2002-01-01

    Complete text of publication follows. We have reported the graft polymerization of vinyl monomers initiated by surface radicals formed by the decomposition of azo and peroxide groups previously introduced onto the surface. In addition, the grafting of polymers onto carbon black has been reported by the reaction of polymer radicals with the surface. On the other hand, it is well known that the relatively stable radicals are generated on the surface by the γ-ray irradiation. In this paper, the grafting of polystyrene onto silica surface during the thermal polymerization of styrene in the presence of γ-ray irradiated silica, grafting mechanism and thermal stability of grafted polymer will be discussed. The grafting of polymers onto silica surface by irradiation of polymer-adsorbed silica was also investigated. Silica obtained from Mitsubishi Chemical Co., Japan was used after pulverization: the particle size was 0.037-0.088 mm. Irradiation was performed in Cs-137 source at room temperature. The silica was irradiated at 50 Gy with dose rate of 3.463 Gy/min. Into a polymerization tube, styrene and irradiated silica was charged and the polymerization was carried out under argon under stirring. The percentage of polystyrene grafting was determined from weight loss when polystyrene-grafted silica was heated at 600 deg C by a thermal analyzer. Untreated silica did not affect the thermal polymerization of styrene. On the contrary, the thermal polymerization of styrene was remarkably retarded in the presence of the irradiated silica at 60 deg C. Similar tendency was reported during the polymerization of vinyl monomers in the presence of carbon black. In the initial stage of the polymerization in the presence of the irradiated silica below 50 deg C, the polymerization was accelerated. During the polymerization in the presence of irradiated silica, polystyrene was grafted onto the surface: the percentage of grafting was 5-11%. The amount of polystyrene grafted onto silica

  10. Synthesis of no-carrier-added radiobrominated n-alkylated analogues of spiperone

    International Nuclear Information System (INIS)

    Moerlein, S.M.; Laufer, P.; Stoecklin, G.

    1985-01-01

    The synthesis of a series of p-bromo-3-N-alkyl spiperone analogues is described. N-alkylation was achieved via reaction of the potassium salt of the spiperone lactam ring with alkyl iodide; subsequent reactions with elemental bromine gave the p-brominated isomers. Optimization studies using no-carrier-added (n.c.a.) 77 Br - indicated that radio-bromination of N-alkyl spiperone analogues occurs with higher yields and in shorter reaction times when dichloramine-T (DCT) is used rather than H 2 0 2 /acetic acid as an oxidant. The production of the title compounds in high effective specific activity with radiochemical yields of 20-30 % using n.c.a. 77 Br - and DCT is reported. (author)

  11. Synthesis and Characterization of Alkylated Bacterial Cellulose in an Ionic Liquid

    Directory of Open Access Journals (Sweden)

    Jinmin Qin

    2015-02-01

    Full Text Available Bacterial cellulose was alkylated by alkyl halide in the ionic liquid 1-butyl-3-methylimmidazolium chloride ([Bmim]Cl with NaH as the alkaline agent. The derivatives were characterized using Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, elemental analyses, X-ray diffraction, and thermal gravimetric analyses. The resultant bacterial cellulose alkylated derivatives (BCADs had a degree of substitution (DS between 0.21 and 2.01. The effects of the alkylating agent, reactant amount, and temperature on the DS were investigated. BCADs with a butyl substituent had a higher DS than did those with ethyl or propyl groups. The crystallinity and thermal stability of the derivatives decreased after modification owing to the change in morphological structure.

  12. Hydrothermal stability of microporous silica and niobia-silica membranes

    NARCIS (Netherlands)

    Boffa, V.; Blank, David H.A.; ten Elshof, Johan E.

    2008-01-01

    The hydrothermal stability of microporous niobia–silica membranes was investigated and compared with silica membranes. The membranes were exposed to hydrothermal conditions at 150 and 200 °C for 70 h. The change of pore structure before and after exposure to steam was probed by single-gas permeation

  13. Ultrasonic Relaxation Study of 1-Alkyl-3-methylimidazolium-Based Room-Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation.

    Science.gov (United States)

    Zorębski, Michał; Zorębski, Edward; Dzida, Marzena; Skowronek, Justyna; Jężak, Sylwia; Goodrich, Peter; Jacquemin, Johan

    2016-04-14

    Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides were determined as a function of the alkyl chain length on the cation from 1-propyl to 1-hexyl from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally, the speed of sound, density, and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e., relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single-Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies.

  14. Serpentinization processes: Influence of silica

    Science.gov (United States)

    Huang, R.; Sun, W.; Ding, X.; Song, M.; Zhan, W.

    2016-12-01

    Serpentinization systems are highly enriched in molecular hydrogen (H2) and hydrocarbons (e.g. methane, ethane and propane). The production of hydrocarbons results from reactions between H2 and oxidized carbon (carbon dioxide and carbon monoxide), which possibly contribute to climate changes during early history of the Earth. However, the influence of silica on the production of H2 and hydrocarbons was poorly constrained. We performed experiments at 311-500 °C and 3.0 kbar using mechanical mixtures of silica and olivine in ratios ranging from 0 to 40%. Molecular hydrogen (H2), methane, ethane and propane were formed, which were analyzed by gas chromatography. It was found that silica largely decreased H2 production. Without any silica, olivine serpentinization produced 94.5 mmol/kg H2 after 20 days of reaction time. By contrast, with the presence of 20% silica, H2 concentrations decreased largely, 8.5 mmol/kg. However, the influence of silica on the production of hydrocarbons is negligible. Moreover, with the addition of 20%-40% silica, the major hydrous minerals are talc, which was quantified according to an established standard curve calibrated by infrared spectroscopy analyses. It shows that silica greatly enhances olivine hydration, especially at 500 °C. Without any addition of silica, reaction extents were serpentinization at 500 °C and 3.0 kbar. By contrast, with the presence of 50% silica, olivine was completely transformed to talc within 9 days. This study indicates that silica impedes the oxidation of ferrous iron into ferric iron, and that rates of olivine hydration in natural geological settings are much faster with silica supply.

  15. Nickel-Catalyzed C–O Bond-Cleaving Alkylation of Esters: Direct Replacement of the Ester Moiety by Functionalized Alkyl Chains

    KAUST Repository

    Liu, Xiangqian; Jia, Jiaqi; Rueping, Magnus

    2017-01-01

    Two efficient protocols for the nickel-catalyzed aryl–alkyl cross-coupling reactions using esters as coupling components have been established. The methods enable the selective oxidative addition of nickel to acyl C–O and aryl C–O bonds and allow the aryl–alkyl cross-coupling via decarbonylative bond cleavage or through cleavage of a C–O bond with high efficiency and good functional group compatibility. The protocols allow the streamlined, unconventional utilization of widespread ester groups and their precursors, carboxylic acids and phenols, in synthetic organic chemistry.

  16. Nickel-Catalyzed C–O Bond-Cleaving Alkylation of Esters: Direct Replacement of the Ester Moiety by Functionalized Alkyl Chains

    KAUST Repository

    Liu, Xiangqian

    2017-06-07

    Two efficient protocols for the nickel-catalyzed aryl–alkyl cross-coupling reactions using esters as coupling components have been established. The methods enable the selective oxidative addition of nickel to acyl C–O and aryl C–O bonds and allow the aryl–alkyl cross-coupling via decarbonylative bond cleavage or through cleavage of a C–O bond with high efficiency and good functional group compatibility. The protocols allow the streamlined, unconventional utilization of widespread ester groups and their precursors, carboxylic acids and phenols, in synthetic organic chemistry.

  17. Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites

    Science.gov (United States)

    Xu, Tiwen; Jia, Zhixin; Luo, Yuanfang; Jia, Demin; Peng, Zheng

    2015-02-01

    The epoxidized natural rubber (ENR) as an interfacial modifier was used to improve the mechanical and dynamical mechanical properties of NR/silica composites. In order to reveal the interaction mechanism between ENR and silica, the ENR/Silica model compound was prepared by using an open mill and the interfacial interaction of ENR with silica was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and stress-strain testing. The results indicated that the ring-opening reaction occurs between the epoxy groups of ENR chains and Si-OH groups on the silica surfaces and the covalent bonds are formed between two phases, which can improve the dispersion of silica in the rubber matrix and enhance the interfacial combination between rubber and silica. The ring-opening reaction occurs not only in vulcanization process but also in mixing process, meanwhile, the latter seems to be more important due to the simultaneous effects of mechanical force and temperature.

  18. Utilizing a sequential injection system furnished with an extraction microcolumn as a novel approach for executing sequential extractions of metal species in solid samples

    DEFF Research Database (Denmark)

    Chomchoei, R.; Hansen, Elo Harald; Shiowatana, J.

    2007-01-01

    This communication presents a novel approach to perform sequential extraction of elements in solid samples by using a sequential injection (SI) system incorporating a specially designed extraction microcolumn. Based on the operation of the syringe pump, different modes of extraction are potentially...... that the system entails many advantages such as being fully automated, and besides being characterised by rapidity, ease of operation and robustness, it is less prone to risks of contamination and personal errors as encountered in traditional batch systems. Moreover, improvement of the precision and accuracy...... of the chemical fractionation of metal in solids as compared with previous reports are obtained. The system ensures that extraction is performed at designated pH values. Variation of sample weight to column volume ratios do not affect the amounts of extractable metals, nor do extraction flow rates ranging from 50...

  19. Leukemia after therapy with alkylating agents for childhood cancer

    International Nuclear Information System (INIS)

    Tucker, M.A.; Meadows, A.T.; Boice, J.D. Jr.

    1987-01-01

    The risk of leukemia was evaluated in 9,170 2-or-more-year survivors of childhood cancer in the 13 institutions of the Late Effects Study Group. Secondary leukemia occurred in 22 nonreferred individuals compared to 1.52 expected, based on general population rates [relative risk (RR) = 14; 95% confidence interval (CI), 9-22]. The influence of therapy for the first cancer on subsequent leukemia risk was determined by a case-control study conducted on 25 cases and 90 matched controls. Treatment with alkylating agents was associated with a significantly elevated risk of leukemia (RR = 4.8; 95% CI, 1.2-18.9). A strong dose-response relationship was also observed between leukemia risk and total dose of alkylating agents, estimated by an alkylator score. The RR of leukemia reached 23 in the highest dose category. Radiation therapy, however, did not increase risk. Although doxorubicin was also identified as a possible risk factor, the excess risk of leukemia following treatment for childhood cancer appears almost entirely due to alkylating agents

  20. Alkylation of imidazole under ultrasound irradiation over alkaline carbons

    International Nuclear Information System (INIS)

    Costarrosa, L.; Calvino-Casilda, V.; Ferrera-Escudero, S.; Duran-Valle, C.J.; Martin-Aranda, R.M.

    2006-01-01

    N-Alkyl-imidazole has been synthesized by sonochemical irradiation of imidazole and 1-bromobutane using alkaline-promoted carbons (exchanged with the binary combinations of Na, K and Cs). The catalysts were characterized by X-ray photoelectron spectroscopy, thermal analysis and N 2 adsorption isotherms. Under the experimental conditions, N-alkyl-imidazoles can be prepared with a high activity and selectivity. It is observed that imidazole conversion increases in parallel with increasing the basicity of the catalyst. The influence of the alkaline promoter, the reaction temperature, and the amount of catalyst on the catalytic activity has been studied. For comparison, the alkylation of imidazole has also been performed in a batch reactor system under thermal activation

  1. Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tiwen [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Jia, Zhixin, E-mail: zxjia@scut.edu.cn [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Luo, Yuanfang; Jia, Demin [College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Peng, Zheng [Agricultural Product Processing Research Institute, Chinese Academy of Tropical Agriculture Sciences, Zhanjiang 524001 (China)

    2015-02-15

    Highlights: • Substantiate the ring open reaction between Si-OH of silica and epoxy groups of ENR. • ENR can act as a bridge between NR and silica to enhance the interfacial interaction. • As a modifier, ENR gets the potential to be used in the tread of green tire for improving the wet skid resistance apparently. - Abstract: The epoxidized natural rubber (ENR) as an interfacial modifier was used to improve the mechanical and dynamical mechanical properties of NR/silica composites. In order to reveal the interaction mechanism between ENR and silica, the ENR/Silica model compound was prepared by using an open mill and the interfacial interaction of ENR with silica was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and stress–strain testing. The results indicated that the ring-opening reaction occurs between the epoxy groups of ENR chains and Si-OH groups on the silica surfaces and the covalent bonds are formed between two phases, which can improve the dispersion of silica in the rubber matrix and enhance the interfacial combination between rubber and silica. The ring-opening reaction occurs not only in vulcanization process but also in mixing process, meanwhile, the latter seems to be more important due to the simultaneous effects of mechanical force and temperature.

  2. Alkyl Radicals as Hydrogen Bond Acceptors: Computational Evidence

    DEFF Research Database (Denmark)

    Hammerum, Steen

    2009-01-01

    Spectroscopic, energetic and structural information obtained by DFT and G3-type computational studies demonstrates that charged proton donors can form moderately strong hydrogen bonds to simple alkyl radicals. The presence of these bonds stabilizes the adducts and modifies their structure......, and gives rise to pronounced shifts of IR stretching frequencies and to increased absorption intensities. The hydrogen bond acceptor properties of alkyl radicals equal those of many conventional acceptors, e.g., the bond length changes and IR red-shifts suggest that tert-butyl radicals are slightly better...... acceptors than formaldehyde molecules, while propyl radicals are as good as H2O. The hydrogen bond strength appears to depend on the proton affinity of the proton donor and on the ionization energy of the acceptor alkyl radical, not on the donor-acceptor proton affinity difference, reflecting...

  3. Polycyclic aromatic acids are primary metabolites of alkyl-PAHs - a case study with Nereis diversicolor

    DEFF Research Database (Denmark)

    Malmquist, Linus Mattias Valdemar; Selck, Henriette; Jørgensen, Kåre Bredeli

    2015-01-01

    Although concentrations of alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) in oil-contaminated sediments are higher than those of unsubstituted PAHs, only little attention has been given to metabolism and ecotoxicity of alkyl-PAHs. In this study we demonstrated that metabolism of alkyl-PA...... that carboxylic acid metabolites of alkyl-PAHs have the potential of constituting a new class of contaminants in marine waters that needs attention in relation to ecological risk assessments.......Although concentrations of alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) in oil-contaminated sediments are higher than those of unsubstituted PAHs, only little attention has been given to metabolism and ecotoxicity of alkyl-PAHs. In this study we demonstrated that metabolism of alkyl...

  4. Extended exposure to alkylator chemotherapy: delayed appearance of myelodysplasia.

    Science.gov (United States)

    Chamberlain, Marc C; Raizer, Jeffrey

    2009-06-01

    A case series of gliomas treated with alkylator-based chemotherapy who subsequently developed myelodysplastic syndrome (tMDS) or acute myelocytic leukemia (AML). Alkylator-based chemotherapy is recognized to be leukemogenic; however, it is infrequently described as a delayed consequence of anti-glioma treatment. Seven patients (4 men; 3 women) ages 34-69 years (median 44), with gliomas (3 Grade 2; 4 Grade 3) were treated with surgery, all but one with involved-field radiotherapy and all with alkylator-based chemotherapy (temozolomide; 6 patients, nitrosoureas; 5 patients, both agents; 5 patients). Exposure to alkylator-based chemotherapy ranged from 8 to 30 months (median 24). The diagnosis of tMDS was determined by bone marrow biopsy in 7 patients. Seven patients showed chromosomal abnormalities consistent with chemotherapy induced MDS. Three patients were diagnosed with AML as well (in two determined by bone marrow and one at autopsy). Interval from last chemotherapy exposure to diagnosis of tMDS/AML ranged from 3 to 31 months (median 24 months). Two patients were treated with bone marrow transplantation and 5 received supportive care only. Five patients have died, 2 as a consequence of recurrent brain tumor, 1 as a complication of transplantation, and 2 due to AML. Although rare, induction of tMDS/AML following extended use of alkylator-based chemotherapy may become more relevant with the evolving practice to treat gliomas for protracted periods. Future work to determine at risk patients would be important.

  5. Study on superhydrophobic surfaces of octanol grafted electrospun silica nanofibers

    International Nuclear Information System (INIS)

    Meng, Long-Yue; Han, Shunyu; Jiang, Nanzhe; Meng, Wan

    2014-01-01

    In this work, superhydrophobic surfaces were successfully prepared by grafting of octanol on the surface of electrospun silica nanofibers (SNFs). The chemical compositions and microstructures of the prepared SNFs surfaces were investigated by using N 2 full isotherms, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and contact angle measurements. The results indicate that the surface of SNFs changed from being superhydrophilic to superhydrophobic by octanol surface grafting. The contact angle of the octanol-grafted SNFs was close to 150.2° because their surface was modified by –(CH 2 ) 6 –CH 3 groups. The 3D network of SNFs networks and the low surface energy of the alkyl side chains played important roles in creating the superhydrophobic surface of the SNFs. - Highlights: • Superhydrophobic surface was prepared from electrospinning SNFs and by grafting octanol on their surface. • The surface of SNFs changed from superhydrophilic to superhydrophobic. • The CA of MSNFs became 150.2° because of interactions between grafted octyl groups

  6. Study on superhydrophobic surfaces of octanol grafted electrospun silica nanofibers

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Long-Yue [Key Laboratory of Natural Resources of Changbai Mountain and Functional Molecules, Yanbian University, Yanji 133002 (China); Department of Chemical Engineering, College of Engineering, Yanbian University, 977 Gongyuan Road, Yanji 133002 (China); Han, Shunyu; Jiang, Nanzhe [Department of Chemical Engineering, College of Engineering, Yanbian University, 977 Gongyuan Road, Yanji 133002 (China); Meng, Wan, E-mail: mengw@ybu.edu.cn [Department of Chemical Engineering, College of Engineering, Yanbian University, 977 Gongyuan Road, Yanji 133002 (China)

    2014-12-15

    In this work, superhydrophobic surfaces were successfully prepared by grafting of octanol on the surface of electrospun silica nanofibers (SNFs). The chemical compositions and microstructures of the prepared SNFs surfaces were investigated by using N{sub 2} full isotherms, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and contact angle measurements. The results indicate that the surface of SNFs changed from being superhydrophilic to superhydrophobic by octanol surface grafting. The contact angle of the octanol-grafted SNFs was close to 150.2° because their surface was modified by –(CH{sub 2}){sub 6}–CH{sub 3} groups. The 3D network of SNFs networks and the low surface energy of the alkyl side chains played important roles in creating the superhydrophobic surface of the SNFs. - Highlights: • Superhydrophobic surface was prepared from electrospinning SNFs and by grafting octanol on their surface. • The surface of SNFs changed from superhydrophilic to superhydrophobic. • The CA of MSNFs became 150.2° because of interactions between grafted octyl groups.

  7. Effect of Amphiphilic Alkyl Chain Length Upon Purified LATEX Stability

    International Nuclear Information System (INIS)

    Amira Amir Hassan; Amir Hashim Mohd Yatim

    2015-01-01

    Rubber particles in purified latex (PL) are stabilized by a film of protein and fatty acid soap (surfactant). Saturated straight-chain fatty acid soaps can assist an enhancement of latex stability. However, whether the alkyl chain length plays an important role in increasing the stability is still an issue. The aim of this study is to investigate the effect of alkyl chain length of anionic surfactant on the stability of purified latex. The fatty acid soap of decanoate (9), laurate (11), sodium dodecyl sulphate (SDS) (12) and palmitate (15) were used. The numbers in parentheses indicating the number of carbon present in alkyl chain of the soap. The results showed that the impact of alkyl chain length on the stability of latex is in the order of laurate > decanoate > SDS > palmitate > purified latex accordingly. The alkyl chain length does giving a significant effect on latex stability after longer stirring time. The particle size of latex with the presence of surfactant is greater compare to a single particle itself due to extension of particles diameter. Thus suitable interaction of the nonpolar tail of surfactant with the hydrophobic regions of latex surface played a major role in maintaining a stable latex system. (author)

  8. C2-Selective Branched Alkylation of Benzimidazoles by Rhodium(I)-Catalyzed C-H Activation.

    Science.gov (United States)

    Tran, Gaël; Confair, Danielle; Hesp, Kevin D; Mascitti, Vincent; Ellman, Jonathan A

    2017-09-01

    Herein, we report a Rh(I)/bisphosphine/K 3 PO 4 catalytic system allowing for the first time the selective branched C-H alkylation of benzimidazoles with Michael acceptors. Branched alkylation with N,N-dimethyl acrylamide was successfully applied to the alkylation of a broad range of benzimidazoles incorporating a variety of N-substituents and with both electron-rich and -poor functionality displayed at different sites of the arene. Moreover, the introduction of a quaternary carbon was achieved by alkylation with ethyl methacrylate. The method was also shown to be applicable to the C2-selective branched alkylation of azabenzimidazoles.

  9. Selective sp3 C–H alkylation via polarity-match-based cross-coupling

    Science.gov (United States)

    Le, Chip; Liang, Yufan; Evans, Ryan W.; Li, Ximing; MacMillan, David W. C.

    2017-01-01

    The functionalization of carbon–hydrogen (C–H) bonds is one of the most attractive strategies for molecular construction in organic chemistry. The hydrogen atom is considered to be an ideal coupling handle, owing to its relative abundance in organic molecules and its availability for functionalization at almost any stage in a synthetic sequence1. Although many C–H functionalization reactions involve C(sp3)–C(sp2) coupling, there is a growing demand for C–H alkylation reactions, wherein sp3 C–H bonds are replaced with sp3 C–alkyl groups. Here we describe a polarity-match-based selective sp3 C–H alkylation via the combination of photoredox, nickel and hydrogen-atom transfer catalysis. This methodology simultaneously uses three catalytic cycles to achieve hydridic C–H bond abstraction (enabled by polarity matching), alkyl halide oxidative addition, and reductive elimination to enable alkyl–alkyl fragment coupling. The sp3 C–H alkylation is highly selective for the α-C–H of amines, ethers and sulphides, which are commonly found in pharmaceutically relevant architectures. This cross-coupling protocol should enable broad synthetic applications in de novo synthesis and late-stage functionalization chemistry. PMID:28636596

  10. Discovery and identification of a series of alkyl decalin isomers in petroleum geological samples.

    Science.gov (United States)

    Wang, Huitong; Zhang, Shuichang; Weng, Na; Zhang, Bin; Zhu, Guangyou; Liu, Lingyan

    2015-07-07

    The comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) has been used to characterize a crude oil and a source rock extract sample. During the process, a series of pairwise components between monocyclic alkanes and mono-aromatics have been discovered. After tentative assignments of decahydronaphthalene isomers, a series of alkyl decalin isomers have been synthesized and used for identification and validation of these petroleum compounds. From both the MS and chromatography information, these pairwise compounds were identified as 2-alkyl-decahydronaphthalenes and 1-alkyl-decahydronaphthalenes. The polarity of 1-alkyl-decahydronaphthalenes was stronger. Their long chain alkyl substituent groups may be due to bacterial transformation or different oil cracking events. This systematic profiling of alkyl-decahydronaphthalene isomers provides further understanding and recognition of these potential petroleum biomarkers.

  11. When alcohol is the answer: Trapping, identifying and quantifying simple alkylating species in aqueous environments.

    Science.gov (United States)

    Penketh, Philip G; Shyam, Krishnamurthy; Baumann, Raymond P; Zhu, Rui; Ishiguro, Kimiko; Sartorelli, Alan C; Ratner, Elena S

    2016-09-01

    Alkylating agents are a significant class of environmental carcinogens as well as commonly used anticancer therapeutics. Traditional alkylating activity assays have utilized the colorimetric reagent 4-(4-nitrobenzyl)pyridine (4NBP). However, 4NBP based assays have a relatively low sensitivity towards harder, more oxophilic alkylating species and are not well suited for the identification of the trapped alkyl moiety due to adduct instability. Herein we describe a method using water as the trapping agent which permits the trapping of simple alkylating electrophiles with a comparatively wide range of softness/hardness and permits the identification of donated simple alkyl moieties. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Gas Separation through Bilayer Silica, the Thinnest Possible Silica Membrane.

    Science.gov (United States)

    Yao, Bowen; Mandrà, Salvatore; Curry, John O; Shaikhutdinov, Shamil; Freund, Hans-Joachim; Schrier, Joshua

    2017-12-13

    Membrane-based gas separation processes can address key challenges in energy and environment, but for many applications the permeance and selectivity of bulk membranes is insufficient for economical use. Theory and experiment indicate that permeance and selectivity can be increased by using two-dimensional materials with subnanometer pores as membranes. Motivated by experiments showing selective permeation of H 2 /CO mixtures through amorphous silica bilayers, here we perform a theoretical study of gas separation through silica bilayers. Using density functional theory calculations, we obtain geometries of crystalline free-standing silica bilayers (comprised of six-membered rings), as well as the seven-, eight-, and nine-membered rings that are observed in glassy silica bilayers, which arise due to Stone-Wales defects and vacancies. We then compute the potential energy barriers for gas passage through these various pore types for He, Ne, Ar, Kr, H 2 , N 2 , CO, and CO 2 gases, and use the data to assess their capability for selective gas separation. Our calculations indicate that crystalline bilayer silica, which is less than a nanometer thick, can be a high-selectivity and high-permeance membrane material for 3 He/ 4 He, He/natural gas, and H 2 /CO separations.

  13. Hybrid ligand-alkylating agents targeting telomeric G-quadruplex structures.

    Science.gov (United States)

    Doria, Filippo; Nadai, Matteo; Folini, Marco; Di Antonio, Marco; Germani, Luca; Percivalle, Claudia; Sissi, Claudia; Zaffaroni, Nadia; Alcaro, Stefano; Artese, Anna; Richter, Sara N; Freccero, Mauro

    2012-04-14

    The synthesis, physico-chemical properties and biological effects of a new class of naphthalene diimides (NDIs) capable of reversibly binding telomeric DNA and alkylate it through an electrophilic quinone methide moiety (QM), are reported. FRET and circular dichroism assays showed a marked stabilization and selectivity towards telomeric G4 DNA folded in a hybrid topology. NDI-QMs' alkylating properties revealed a good reactivity on single nucleosides and selectivity towards telomeric G4. A selected NDI was able to significantly impair the growth of melanoma cells by causing telomere dysfunction and down-regulation of telomerase expression. These findings points to our hybrid ligand-alkylating NDIs as possible tools for the development of novel targeted anticancer therapies. This journal is © The Royal Society of Chemistry 2012

  14. 40 CFR 721.10143 - Amines, bis (C11-14-branched and linear alkyl).

    Science.gov (United States)

    2010-07-01

    ... linear alkyl). 721.10143 Section 721.10143 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10143 Amines, bis (C11-14-branched and linear alkyl). (a) Chemical..., bis (C11-14-branched and linear alkyl) (PMN P-06-733; CAS No. 900169-60-0) is subject to reporting...

  15. Alkylation damage causes MMR-dependent chromosomal instability in vertebrate embryos.

    NARCIS (Netherlands)

    Feitsma, H.; Akay, A.; Cuppen, E.

    2008-01-01

    S(N)1-type alkylating agents, like N-methyl-N-nitrosourea (MNU) and N-ethyl-N-nitrosourea (ENU), are potent mutagens. Exposure to alkylating agents gives rise to O(6)-alkylguanine, a modified base that is recognized by DNA mismatch repair (MMR) proteins but is not repairable, resulting in

  16. Natural and bioremediated selective degradation of polycyclic aromatic alkyl isomers in oil-contaminated soils

    International Nuclear Information System (INIS)

    Sauer, T.C.; McCarthy, K.; Uhler, A.; Porta, A.

    1995-01-01

    In studies where 2- to 6-ring polycyclic aromatic hydrocarbons (PAHs) are determined as part of characterizing released oil constituents in environmental samples, the changes in composition of PAHs from weathering (e.g., evaporation, dissolution) and biodegradation are most often represented by PAH alkyl homologue distributions. Concentrations of PAH alkyl groups are the sum of individual PAH isomers of similar carbon number; such as for C2-naphthalenes, the C2 alkyl group consists of dimethyl and ethyl substitutions on the parent naphthalene. In weathering and degradation studies, the changes in relative concentration of the individual isomers within an alkyl group are rarely reported. In a field study of oiled soils, the authors looked at the selective losses, for a period of a year, of individual PAH alkyl isomers that occur both naturally by weathering processes and through the use of bioremediation technology. Results showed that decreases in alkyl group concentrations were not always represented by similar losses of each isomer in the alkyl group, but were often due to the preferential or selective loss of certain isomers in the group

  17. Gold-catalyzed alkylation of silyl enol ethers with ortho-alkynylbenzoic acid esters

    Directory of Open Access Journals (Sweden)

    Yoshinori Yamamoto

    2011-05-01

    Full Text Available Unprecedented alkylation of silyl enol ethers has been developed by the use of ortho-alkynylbenzoic acid alkyl esters as alkylating agents in the presence of a gold catalyst. The reaction probably proceeds through the gold-induced in situ construction of leaving groups and subsequent nucleophilic attack on the silyl enol ethers. The generated leaving compound abstracts a proton to regenerate the silyl enol ether structure.

  18. Thermochemical investigation into coordination ability of zinc and cadmium alkyl compounds in solutions

    International Nuclear Information System (INIS)

    Aleksandrov, Yu.A.; Fedostseva, G.A.; Tsvetkov, V.G.; Lebedev, S.A.; Kozyrkin, B.I.

    1983-01-01

    Enthalpies of zinc alkyl compounds mixing, as well as those of dimethyl cadmium mixing with hexane, previously used as a solvent during the study of liquid-phase autooxidation of Me 2 Cd and Me 2 Zn, and with a series of organic bases at 298 K and at components ratio 1:1 or 1:2, are determined. Using calorimetric method dimethyl cadmium association in liquid state has been evaluated. Coordination ability of zinc alkyl compounds is higher than for the corresponding cadmium compounds. With the increase of alkyl radical length the electron seeking ability of zinc compounds decreases. On the basis of thermochemical data relative stability of coordination compounds of zinc and cadmium alkyl compounds with certain alkyl compounds of group 6 elements is evaluated: it has the maximum value for sulfur compounds

  19. Synthesis of uniform carbon at silica nanocables and luminescent silica nanotubes with well controlled inner diameters

    International Nuclear Information System (INIS)

    Qian Haisheng; Yu Shuhong; Ren Lei; Yang Yipeng; Zhang Wei

    2006-01-01

    Uniform carbon at silica nanocables and silica nanotubes with well-controlled inner diameters can be synthesized in an easy way by a sacrificial templating method. This was performed using carbon nanofibres as hard templates that were synthesized previously by a hydrothermal carbonization process. Silica nanotubes with well-controlled inner diameters were synthesized from carbon at silica core-shell nanostructures by removal of the core carbon component. The inner diameters of the as-prepared silica nanotubes can be well controlled from several nanometres to hundreds of nanometres by adjusting the diameters of the carbon nanofibres. The silica nanotubes synthesized by this method display strong photoluminescence in ultraviolet at room temperature. Such uniform silica nanotubes might find potential applications in many fields such as encapsulation, catalysis, chemical/biological separation, and sensing

  20. Silica/Perfluoropolymer nanocomposites fabricated by direct melt-compounding: a novel method without surface modification on nano-silica.

    Science.gov (United States)

    Tanahashi, Mitsuru; Hirose, Masaki; Watanabe, Yusuke; Lee, Jeong-Chang; Takeda, Kunihiko

    2007-07-01

    A novel method for the fabrication of silica/perfluoropolymer nanocomposites was investigated, whereby nano-sized silica particles without surface modification were dispersed uniformly through mechanical breakdown of loosely packed agglomerates of silica nanoparticles with low fracture strength in a polymer melt during direct melt-compounding. The method consists of two stages. The first stage involves preparation of the loose silica agglomerate, and the second stage involves melt-compounding of a completely hydrophobic perfluoropolymer, poly(tetrafluoroethyleneco-perfluoropropylvinylether), with the loose silica agglomerates prepared in the first stage. In the first stage, the packing structure and the fracture strength of the silica agglomerate were controlled by destabilizing an aqueous colloidal silica solution with a mean primary diameter of 190 nm via pH control and salt addition. In the next stage, the silica/perfluoropolymer nanocomposite was fabricated by breaking down the prepared loose silica agglomerates with low fracture strength by means of a shear force inside the polymer melt during melt-compounding.

  1. Solid-Phase S-Alkylation Promoted by Molecular Sieves.

    Science.gov (United States)

    Calce, Enrica; Leone, Marilisa; Mercurio, Flavia Anna; Monfregola, Luca; De Luca, Stefania

    2015-11-20

    A solid-phase S-alkylation procedure to introduce chemical modification on the cysteine sulfhydryl group of a peptidyl resin is reported. The reaction is promoted by activated molecular sieves and consists of a solid-solid process, since both the catalyst and the substrate are in a solid state. The procedure was revealed to be efficient and versatile, particularly when used in combination with the solution S-alkylation approach, allowing for the introduction of different molecular diversities on the same peptide molecule.

  2. Improved detection of hydrophilic phosphopeptides using graphite powder microcolumns and mass spectrometry: evidence for in vivo doubly phosphorylated dynamin I and dynamin III

    DEFF Research Database (Denmark)

    Larsen, Martin Røssel; Graham, Mark E; Robinson, Phillip J

    2004-01-01

    A common strategy in proteomics to improve the number and quality of peptides detected by mass spectrometry (MS) is to desalt and concentrate proteolytic digests using reversed phase (RP) chromatography prior to analysis. However, this does not allow for detection of small or hydrophilic peptides...... a large improvement in the detection of small amounts of phosphopeptides by MS and the approach has major implications for both small- and large-scale projects in phosphoproteomics.......A common strategy in proteomics to improve the number and quality of peptides detected by mass spectrometry (MS) is to desalt and concentrate proteolytic digests using reversed phase (RP) chromatography prior to analysis. However, this does not allow for detection of small or hydrophilic peptides......, or peptides altered in hydrophilicity such as phosphopeptides. We used microcolumns to compare the ability of RP resin or graphite powder to retain phosphopeptides. A number of standard phosphopeptides and a biologically relevant phosphoprotein, dynamin I, were analyzed. MS revealed that some phosphopeptides...

  3. From old alkylating agents to new minor groove binders.

    Science.gov (United States)

    Puyo, Stéphane; Montaudon, Danièle; Pourquier, Philippe

    2014-01-01

    Alkylating agents represent the oldest class of anticancer agents with the approval of mechloretamine by the FDA in 1949. Even though their clinical use is far beyond the use of new targeted therapies, they still occupy a major place in the treatment of specific malignancies, sometimes representing the unique option for the treatment of refractory tumors. Here, we are reviewing the major classes of alkylating agents, with a particular focus on the latest generations of compounds that specifically target the minor groove of the DNA. These naturally occurring derivatives have a unique mechanism of action that explains the recent regain of interest in developing new classes of alkylating agents that could be used in combination with other anticancer drugs to enhance tumor response in the clinic. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  4. Sonochemical coating of magnetite nanoparticles with silica.

    Science.gov (United States)

    Dang, Feng; Enomoto, Naoya; Hojo, Junichi; Enpuku, Keiji

    2010-01-01

    Magnetite nanoparticles were coated with silica through the hydrolysis and condensation of tetraethyl orthosilicate (TEOS) under ultrasonic irradiation. The ultrasonic irradiation was used to prevent the agglomeration of the magnetite particles and accelerate the hydrolysis and condensation of TEOS. TEM, DLS, XRF, VSM, TG and sedimentation test were used to characterize the silica-coated magnetite particles. The dispersibility of silica-coated magnetite particles in aqueous solution was improved significantly and the agglomerate particle size was decreased to 110 nm. It was found that the agglomerate particle size of silica-coated magnetite particles was mainly decided by the coating temperature and the pH value in the silica-coating process. The weight ratio of silica in silica-coated magnetite particles was mainly decided by the pH value in the silica-coating process. The dispersibility of silica-coated magnetite particles was mainly decided by the agglomerate particle size of the suspension. The oxidation of magnetite particles in air was limited through the coated silica. The magnetism of silica-coated magnetite particles decreased slightly after silica-coating.

  5. Methods of producing alkylated hydrocarbons from an in situ heat treatment process liquid

    Science.gov (United States)

    Roes, Augustinus Wilhelmus Maria [Houston, TX; Mo, Weijian [Sugar Land, TX; Muylle, Michel Serge Marie [Houston, TX; Mandema, Remco Hugo [Houston, TX; Nair, Vijay [Katy, TX

    2009-09-01

    A method for producing alkylated hydrocarbons is disclosed. Formation fluid is produced from a subsurface in situ heat treatment process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. The liquid stream is fractionated to produce at least a second gas stream including hydrocarbons having a carbon number of at least 3. The first gas stream and the second gas stream are introduced into an alkylation unit to produce alkylated hydrocarbons. At least a portion of the olefins in the first gas stream enhance alkylation.

  6. Method of removing alkyl iodides or mixtures of iodine and alkyl iodides from a gas phase and an aqueous solution phase by utilizing ion exchange resins

    International Nuclear Information System (INIS)

    Shimizu, Hiroshi; Mizuuchi, Noboru; Yokoyama, Fumio.

    1967-01-01

    Alkyl iodides and mixtures of iodine and alkyl iodides are removed from a gas phase and an aquous solution phase by using solely an anion exchange resin containing a tertiary amine or together with an anion exchange resin containing quarternary ammonium compound. The resin containing the quarternary ammonium compound is employed mainly to remove iodine, and the resin containing the tertiary amine serves mainly to remove alkyl iodides. The method can be applied to collecting a majority of the methyl iodide as well as the radioactive iodine produced in the atmosphere of a reactor in case of a fuel accident. In embodiments, it is desirable to maintain the sufficient moisture content of the anion exchange resins at a sufficient moisture level so as not to reduce the migration speed of the iodine and alkyl iodides. The iodine and alkyl iodide can be produced with high efficiency and stability independently of the relative humidity of the gas phase. In examples, a solution which consists of 20.5 mg/l of iodine and 42.2mg/l of methyl iodide flew through a column of Amberite IRA-93 alone or blended with IRA-900 at a speed of 15 /hr. respectively. The resins were able to treat 400 times their equivalent in water. (Iwakiri, K.)

  7. Alkyl-halogenide promoted ionic liquid catalysis of isobutane/butene-alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Schilder, L.; Korth, W.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2011-07-01

    The effect of two different types of promoters on the performance of Lewis-acidic chloroaluminate ionic liquid catalysts was studied for liquid liquid biphasic isobutane/2-butene alkylation. In particular, the activity and selectivity of such catalytic systems was investigated. Experimental results obtained from a batch reactor show, that tert-butyl halides increase the reaction rate significantly and shift the C8-selectivity towards the desired high-octane trimethylpentanes (TMPs). But, secondary reactions like oligomerization and cracking are not affected by the use of these promoters. (orig.)

  8. An Efficient Synthesis of 1-Alkyl-2-phenyl-4-quinolones from 2-Halobenzoic Acids

    International Nuclear Information System (INIS)

    Song, Yoon Ju; Choi, Jin Sun; Lee, Jae In

    2013-01-01

    The present method offers an efficient synthesis of 1-alkyl-2-phenyl-4-quinolones from 2-haloben-zoic acids. It has the advantages with respect to (i) synthesis of 2 equiv of alkynones 5 from 1 equiv of 4,6-pyrimidyl di(2-halobenzoates) 3, (ii) synthesis of versatile 1-alkyl-2-phenyl-4-quinolones in high overall yields, and (iii) use of readily available and cheap starting materials. Therefore, this method could be utilized as a practical synthesis of 1-alkyl-2-phenyl-4-quinolones. Several methods have been developed to synthesize 1-alkyl-2-phenyl-4-quinolones from 2'-substituted acetophenones, anilines, and 2-halobenzoyl chlorides as starting materials. The reaction of N-methylisatoic anhydride with the lithium enolate of an 4'-methoxyacetophenone afforded the 1-methyl-2-phenyl-4-quinolone in a short sequence, but the yield was low. N-(2-Acetylphenyl)benzamides, prepared by Friedel-Crafts acylation of N-phenyl benzamides with acetyl chloride or benzoylation of 2'-aminoacetophenones with benzoyl chlorides,8 were cyclized with potassium t-butoxide to yield 2-aryl-4-quinolones, which were further alkylated with alkyl iodides to give 1-alkyl-2-aryl-4-quinolones

  9. An Efficient Synthesis of 1-Alkyl-2-phenyl-4-quinolones from 2-Halobenzoic Acids

    Energy Technology Data Exchange (ETDEWEB)

    Song, Yoon Ju; Choi, Jin Sun; Lee, Jae In [Duksung Women' s Univ., Seoul (Korea, Republic of)

    2013-10-15

    The present method offers an efficient synthesis of 1-alkyl-2-phenyl-4-quinolones from 2-haloben-zoic acids. It has the advantages with respect to (i) synthesis of 2 equiv of alkynones 5 from 1 equiv of 4,6-pyrimidyl di(2-halobenzoates) 3, (ii) synthesis of versatile 1-alkyl-2-phenyl-4-quinolones in high overall yields, and (iii) use of readily available and cheap starting materials. Therefore, this method could be utilized as a practical synthesis of 1-alkyl-2-phenyl-4-quinolones. Several methods have been developed to synthesize 1-alkyl-2-phenyl-4-quinolones from 2'-substituted acetophenones, anilines, and 2-halobenzoyl chlorides as starting materials. The reaction of N-methylisatoic anhydride with the lithium enolate of an 4'-methoxyacetophenone afforded the 1-methyl-2-phenyl-4-quinolone in a short sequence, but the yield was low. N-(2-Acetylphenyl)benzamides, prepared by Friedel-Crafts acylation of N-phenyl benzamides with acetyl chloride or benzoylation of 2'-aminoacetophenones with benzoyl chlorides,8 were cyclized with potassium t-butoxide to yield 2-aryl-4-quinolones, which were further alkylated with alkyl iodides to give 1-alkyl-2-aryl-4-quinolones.

  10. Sequence-selective single-molecule alkylation with a pyrrole-imidazole polyamide visualized in a DNA nanoscaffold.

    Science.gov (United States)

    Yoshidome, Tomofumi; Endo, Masayuki; Kashiwazaki, Gengo; Hidaka, Kumi; Bando, Toshikazu; Sugiyama, Hiroshi

    2012-03-14

    We demonstrate a novel strategy for visualizing sequence-selective alkylation of target double-stranded DNA (dsDNA) using a synthetic pyrrole-imidazole (PI) polyamide in a designed DNA origami scaffold. Doubly functionalized PI polyamide was designed by introduction of an alkylating agent 1-(chloromethyl)-5-hydroxy-1,2-dihydro-3H-benz[e]indole (seco-CBI) and biotin for sequence-selective alkylation at the target sequence and subsequent streptavidin labeling, respectively. Selective alkylation of the target site in the substrate DNA was observed by analysis using sequencing gel electrophoresis. For the single-molecule observation of the alkylation by functionalized PI polyamide using atomic force microscopy (AFM), the target position in the dsDNA (∼200 base pairs) was alkylated and then visualized by labeling with streptavidin. Newly designed DNA origami scaffold named "five-well DNA frame" carrying five different dsDNA sequences in its cavities was used for the detailed analysis of the sequence-selectivity and alkylation. The 64-mer dsDNAs were introduced to five individual wells, in which target sequence AGTXCCA/TGGYACT (XY = AT, TA, GC, CG) was employed as fully matched (X = G) and one-base mismatched (X = A, T, C) sequences. The fully matched sequence was alkylated with 88% selectivity over other mismatched sequences. In addition, the PI polyamide failed to attach to the target sequence lacking the alkylation site after washing and streptavidin treatment. Therefore, the PI polyamide discriminated the one mismatched nucleotide at the single-molecule level, and alkylation anchored the PI polyamide to the target dsDNA.

  11. Silica reinforced triblock copolymer gels

    DEFF Research Database (Denmark)

    Theunissen, E.; Overbergh, N.; Reynaers, H.

    2004-01-01

    The effect of silica and polymer coated silica particles as reinforcing agents on the structural and mechanical properties of polystyrene-poly(ethylene/butylene)-polystyrene (PS-PEB-PS) triblock gel has been investigated. Different types of chemically modified silica have been compared in order...

  12. Effect of silica concentration on electrical conductivity of epoxy resin-carbon black-silica nanocomposites

    International Nuclear Information System (INIS)

    Zhang Wei; Blackburn, Richard S.; Dehghani-Sanij, Abbas A.

    2007-01-01

    Electrical properties of nanocomposites are determined by the conductive paths of carbon black and influenced by a 'network' of silica. With increasing content of silica, carbon black (CB) particles are optimally dispersed, contributing to the generation of a conductive network between CB particles via direct particle contact and a tunneling effect; maximum conductivity for the epoxy resin-CB-silica nanocomposite described herein occurs at a ratio of 0.6:1.0 (SiO 2 :CB). As a non-conductive component, excessive silica will prevent electron flow, giving rise to low conductivity

  13. An in-situ FTIR study of the side-chain alkylation of toluene with methanol

    International Nuclear Information System (INIS)

    King, S.T.; Garces, J.

    1985-01-01

    The side-chain alkylation of toluene with methanol to styrene and ethylbenzene can be an economically attractive industrial process if it has high enough conversion and selectivity. This process has been investigated by many others using zeolites or metal oxides as the catalyst. It has been generally accepted that high basicity in certain size pores in the catalyst is required for such side-chain alkylation. However, the actual reaction mechanism is still not understood. In this paper the results of an in-situ FT-IR study of the side-chain alkylation in Li, Na, K, Rb and Cs exchanged X zeolites is discussed. It was found that the KX, RbX and CsX zeolites, which are capable of side-chain alkylation, also form surface formate and a surface precursor of formate from methanol decomposition. While the surface formate itself is not the alkylation agent, the observed formate precursor may be the intermediate for side-chain alkylation

  14. Thermodynamic Interactions between Polystyrene and Long-Chain Poly(n-Alkyl Acrylates) Derived from Plant Oils.

    Science.gov (United States)

    Wang, Shu; Robertson, Megan L

    2015-06-10

    Vegetable oils and their fatty acids are promising sources for the derivation of polymers. Long-chain poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) are readily derived from fatty acids through conversion of the carboxylic acid end-group to an acrylate or methacrylate group. The resulting polymers contain long alkyl side-chains with around 10-22 carbon atoms. Regardless of the monomer source, the presence of alkyl side-chains in poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) provides a convenient mechanism for tuning their physical properties. The development of structured multicomponent materials, including block copolymers and blends, containing poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) requires knowledge of the thermodynamic interactions governing their self-assembly, typically described by the Flory-Huggins interaction parameter χ. We have investigated the χ parameter between polystyrene and long-chain poly(n-alkyl acrylate) homopolymers and copolymers: specifically we have included poly(stearyl acrylate), poly(lauryl acrylate), and their random copolymers. Lauryl and stearyl acrylate were chosen as model alkyl acrylates derived from vegetable oils and have alkyl side-chain lengths of 12 and 18 carbon atoms, respectively. Polystyrene is included in this study as a model petroleum-sourced polymer, which has wide applicability in commercially relevant multicomponent polymeric materials. Two independent methods were employed to measure the χ parameter: cloud point measurements on binary blends and characterization of the order-disorder transition of triblock copolymers, which were in relatively good agreement with one another. The χ parameter was found to be independent of the alkyl side-chain length (n) for large values of n (i.e., n > 10). This behavior is in stark contrast to the n-dependence of the χ parameter predicted from solubility parameter theory. Our study complements prior work investigating the interactions between

  15. SERIES: Genomic instability in cancer Balancing repair and tolerance of DNA damage caused by alkylating agents

    Science.gov (United States)

    Fu, Dragony; Calvo, Jennifer A.; Samson, Leona D

    2013-01-01

    Alkylating agents comprise a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER), and mismatch repair (MMR) respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial for an organism's favorable response to alkylating agents. Furthermore, an individual's response to alkylating agents can vary considerably from tissue to tissue and from person to person, pointing to genetic and epigenetic mechanisms that modulate alkylating agent toxicity. PMID:22237395

  16. Bifunctional rhodium intercalator conjugates as mismatch-directing DNA alkylating agents.

    Science.gov (United States)

    Schatzschneider, Ulrich; Barton, Jacqueline K

    2004-07-21

    A conjugate of a DNA mismatch-specific rhodium intercalator, containing the bulky chrysenediimine ligand, and an aniline mustard has been prepared, and targeting of mismatches in DNA by this conjugate has been examined. The preferential alkylation of mismatched over fully matched DNA is found by a mobility shift assay at concentrations where untethered organic mustards show little reaction. The binding site of the Rh intercalator was determined by DNA photocleavage, and the position of covalent modification was established on the basis of the enhanced depurination associated with N-alkylation. The site-selective alkylation at mismatched DNA renders these conjugates useful tools for the covalent tagging of DNA base pair mismatches and new chemotherapeutic design.

  17. Ultra narrow bore thick film capillaries for microcolumn separations. Part 1. GC experiments

    NARCIS (Netherlands)

    Steenackers, D.; Sandra, P.J.F.; Sandra, P.; Devos, G.

    1993-01-01

    Ultra narrow bore (50 mum 1.0.) fused silica columns were statically coated with apolar stationary phases to obtain beta values ranging from 6.25 to 50 (filmthickness 2 to 0.25 mum). Performance of the 1 and 2 mum columns in Capillary Gas Chromatography (CGC) is highlighted.

  18. Phosphorus-containing podands. 14. Effect of alkyl substituents at phosphorus atom on complexing ability of neutral monopodands. On the nature of abnormal alkyl effect

    International Nuclear Information System (INIS)

    Tsvetkov, E.N.; Evreinov, V.I.; Bondarenko, N.A.; Safronova, Z.V.

    1996-01-01

    The previously revealed unusual effect of alkyl substituents at phosphorus atom in phosphorus-containing monopodands of the general formula o-R 2 P(O)C 6 H 4 (OCH 2 CH 2 ) n OC 6 H 4 P(O)R 2 -o, n=1-5, R = Alk, Ph, OEt on their complexing ability towards alkali metals cations has been interpreted. Alkyl radicals create great spatial obstacles to rotation of R 2 P(O) fragments around the C-P bond as compared with other substituents, which gives rise to the appearance of anomalous alkyl effect. Solvation is an additional factor, which can bring about the anomalous effect appearance or a change in the degree of its pronouncement. 47 refs.; 3 figs.; 7 tabs

  19. Poly(ethyleneoxide) functionalization through alkylation

    Science.gov (United States)

    Sivanandan, Kulandaivelu; Eitouni, Hany Basam; Li, Yan; Pratt, Russell Clayton

    2015-04-21

    A new and efficient method of functionalizing high molecular weight polymers through alkylation using a metal amide base is described. This novel procedure can also be used to synthesize polymer-based macro-initiators containing radical initiating groups at the chain-ends for synthesis of block copolymers.

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

    Science.gov (United States)

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

    2017-04-01

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

  1. Alkylation and arylation of alkenes by transition metal complexes

    International Nuclear Information System (INIS)

    Volkova, L.G.; Levitin, I.Ya.; Vol'pin, M.E.

    1975-01-01

    In this paper are reviewed methods of alkylation and irylation of unsaturated compounds with complexes of transition metals (Rh, Pd). Analysis of alkylation and arylation of olefines with organic derivatives of transition metals, obtained as a result of exchange reactions between organic compounds of transition metals and salts of metals of the 8th group of the periodic system, allows a conclusion as to the wide possibilities of these reactions in the synthesis of various derivatives of unsaturated compounds. In all the reactions under consideration, intermediate formation of sigma-complexes is assumed. Also considered are alkylation and arylation of olefines with organic derivatives of halogens in the presence of compounds of metals of the 8th group of the periodic system, as well as arylation of olefines with aromatic compounds in the presence of salts of transition metals

  2. Experimental and QSAR study on the surface activities of alkyl imidazoline surfactants

    Science.gov (United States)

    Kong, Xiangjun; Qian, Chengduo; Fan, Weiyu; Liang, Zupei

    2018-03-01

    15 alkyl imidazoline surfactants with different structures were synthesized and their critical micelle concentration (CMC) and surface tension under the CMC (σcmc) in aqueous solution were measured at 298 K. 54 kinds of molecular structure descriptors were selected as independent variables and the quantitative structure-activity relationship (QSAR) between surface activities of alkyl imidazoline and molecular structure were built through the genetic function approximation (GFA) method. Experimental results showed that the maximum surface excess of alkyl imidazoline molecules at the gas-liquid interface increased and the area occupied by each surfactant molecule and the free energies of micellization ΔGm decreased with increasing carbon number (NC) of the hydrophobic chain or decreasing hydrophilicity of counterions, which resulted in a CMC and σcmc decrease, while the log CMC and NC had a linear relationship and a negative correlation. The GFA-QSAR model, which was generated by a training set composed of 13 kinds of alkyl imidazoline though GFA method regression analysis, was highly correlated with predicted values and experimental values of the CMC. The correlation coefficient R was 0.9991, which means high prediction accuracy. The prediction error of 2 kinds of alkyl imidazoline CMCs in the Validation Set that quantitatively analyzed the influence of the alkyl imidazoline molecular structure on the CMC was less than 4%.

  3. Silica particles and method of preparation thereof

    NARCIS (Netherlands)

    2015-01-01

    The invention is in the field of silica products. More in particular, the invention is in the field of amorphous silica particles. The invention is directed to amorphous silica particles and related products including clusters of said silica particles, a suspension of said silica particles, and an

  4. Isobutane/2-butene alkylation over potential heterogeneous catalysts in a slurry reactor

    Energy Technology Data Exchange (ETDEWEB)

    Roervik, T.

    1996-12-31

    The trend towards more effective use of fossil fuels and reduced environmental pollution represents a major task of improvement within the refinery processes. The highly isomerized and high octane paraffins produced from isobutane and light olefins by alkylation fulfill all the requirements for reformulated gasoline. This doctoral thesis discusses new catalyst systems because of their potential in alkylation. A slurry reactor apparatus for solid-acid catalysed isobutane/butene alkylation was developed and used to investigate the performance of various heterogeneous catalysts. The selected materials were mainly zeolite types with faujasite structures. The samples were characterized by various methods before alkylation. In general, the order of decreasing catalyst activity after 3 h of reaction at 80{sup o}C was found to be: H-EMT >> H-FAU, dealuminated H-FAU >> NS.500, TA-Y, CeY-98 > Nafion-H. The order of decreasing alkylate selectivity of the catalysts was: H-EMT >> dealuminated H-FAU > H-FAU >> Nafion-H > CeY-98 > TA-Y > H-SAPO-37, NS.500. H-EMT was the most promising system for further development, also because of the very low formation of the undesirable isooctenes and a high selectivity towards isooctanes among the alkylates. A high density of accessible strong acid sites was found to be essential for a high alkylation activity and selectivity. Open structure, like hexagonal faujasite, was advantageous. The distribution of trimethylpentanes formed in zeolites was ascribed to pore restrictions as a major factor. The effect of operating conditions on catalyst performance was investigated statistically, and a high dilution of butene in the slurry reactor was found to be very important. 153 refs., 40 figs., 12 tabs.

  5. Iminium Salts by Meerwein Alkylation of Ehrlich’s Aldehyde

    Directory of Open Access Journals (Sweden)

    Gerhard Laus

    2013-03-01

    Full Text Available 4-(Dimethylaminobenzaldehyde is alkylated at the N atom by dialkyl sulfates, MeI, or Me3O BF4. In contrast, ethylation by Et3O BF4 occurs selectively at the O atom yielding a quinoid iminium ion. 4-(Diethylaminobenzaldehyde is alkylated only at O by either Et or Me oxonium reagent. The iminium salts are prone to hydrolysis giving the corresponding hydrotetrafluoroborates. Five crystal structures were determined.

  6. Solid acid zeolite catalysts for benzene/ ethylene alkylation reactions

    OpenAIRE

    2011-01-01

    Alkylation of benzene with ethylene to ethylbenzene is widely used in the petrochemical industry. Ethylbenzene is an important raw material in the petrochemical industry. It is used as feedstock for the production of styrene, an important material for plastic and rubber production.The conventional catalyst for this alkylation process is AlCl₃, which accounted for 24% of the worldwide ethylbenzene production in 2009.As utilization of this catalyst involves problems with separation, handling, s...

  7. Persistence of DNA adducts, hypermutation and acquisition of cellular resistance to alkylating agents in glioblastoma.

    Science.gov (United States)

    Head, R J; Fay, M F; Cosgrove, L; Y C Fung, K; Rundle-Thiele, D; Martin, J H

    2017-12-02

    Glioblastoma is a lethal form of brain tumour usually treated by surgical resection followed by radiotherapy and an alkylating chemotherapeutic agent. Key to the success of this multimodal approach is maintaining apoptotic sensitivity of tumour cells to the alkylating agent. This initial treatment likely establishes conditions contributing to development of drug resistance as alkylating agents form the O 6 -methylguanine adduct. This activates the mismatch repair (MMR) process inducing apoptosis and mutagenesis. This review describes key juxtaposed drivers in the balance between alkylation induced mutagenesis and apoptosis. Mutations in MMR genes are the probable drivers for alkylation based drug resistance. Critical to this interaction are the dose-response and temporal interactions between adduct formation and MMR mutations. The precision in dose interval, dose-responses and temporal relationships dictate a role for alkylating agents in either promoting experimental tumour formation or inducing tumour cell death with chemotherapy. Importantly, this resultant loss of chemotherapeutic selective pressure provides opportunity to explore novel therapeutics and appropriate combinations to minimise alkylation based drug resistance and tumour relapse.

  8. COOH-functionalisation of silica particles

    Energy Technology Data Exchange (ETDEWEB)

    Majewski, Peter, E-mail: peter.majewski@unisa.edu.au [School of Advanced Manufacturing and Mechanical Engineering, Mawson Institute, University of South Australia, Adelaide (Australia); Albrecht, Trent [Ian Wark Research Institute, University of South Australia, Adelaide (Australia); Weber, Siegfried [Department of Biotechnology, University of Applied Sciences, Mannheim (Germany)

    2011-09-01

    In this study COOH-functionalised silica is synthesised using phosphonateN-(phosphonomethyl)iminodiacetic acid (PMIDA) in an aqueous solution. The presence of PMIDA on the silica particles was verified using Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy and titration. Experimentally, surface concentrations of COOH functional groups of up to about 3 mmol/g{sub silica} were achieved, whereas theoretical calculation of the maximum COOH functional group concentration gave about 1 mmol/g{sub silica}. The discrepancy may be caused by PMIDA multilayer formation on the particle.

  9. A Theoretical Study of the Mechanism of the Alkylation of Guanine by N- Nitroso Compounds.

    Science.gov (United States)

    1992-01-01

    these chemical agents alkylate DNA, but, as yet, the precise mechanism is unknown. What is known is that the result is a DNA-mutagen adduct with an alkyl ... nitrosoureas , Singer et. al. found that about 25% of the alkylation caused by MNU was on the DNA phospate backbone while, for ENU, phosphate...sites. 1.3 Mutagenicity of N-Nitroso Compounds In early experimental work with agents which alkylate DNA, comparisons of ultraviolet absorption

  10. Charge properties and bacterial contact-killing of hyperbranched polyurea-polyethyleneimine coatings with various degrees of alkylation

    Science.gov (United States)

    Roest, Steven; van der Mei, Henny C.; Loontjens, Ton J. A.; Busscher, Henk J.

    2015-11-01

    Coatings of immobilized-quaternary-ammonium-ions (QUAT) uniquely kill adhering bacteria upon contact. QUAT-coatings require a minimal cationic-charge surface density for effective contact-killing of adhering bacteria of around 1014 cm-2. Quaternization of nitrogen is generally achieved through alkylation. Here, we investigate the contribution of additional alkylation with methyl-iodide to the cationic-charge density of hexyl-bromide alkylated, hyperbranched polyurea-polyethyleneimine coatings measuring charge density with fluorescein staining. X-ray-photoelectron-spectroscopy was used to determine the at.% alkylated-nitrogen. Also streaming potentials, water contact-angles and bacterial contact-killing were measured. Cationic-charge density increased with methyl-iodide alkylation times up to 18 h, accompanied by an increase in the at.% alkylated-nitrogen. Zeta-potentials became more negative upon alkylation as a result of shielding of cationiccharges by hydrophobic alkyl-chains. Contact-killing of Gram-positive Staphylococci only occurred when the cationic-charge density exceeded 1016 cm-2 and was carried by alkylated-nitrogen (electron-binding energy 401.3 eV). Gram-negative Escherichia coli was not killed upon contact with the coatings. There with this study reveals that cationic-charge density is neither appropriate nor sufficient to determine the ability of QUAT-coatings to kill adhering bacteria. Alternatively, the at.% of alkylated-nitrogen at 401.3 eV is proposed, as it reflects both cationic-charge and its carrier. The at.% N401.3 eV should be above 0.45 at.% for Gram-positive bacterial contact-killing.

  11. On-line preconcentration system using a microcolumn packed with Alizarin Red S-modified alumina for zinc determination by flame atomic absorption spectrometry

    Directory of Open Access Journals (Sweden)

    A.M. Haji Shabani

    2009-01-01

    Full Text Available A simple and sensitive on-line flow injection system for determination of zinc with FAAS has been described. The method is based on the separation and preconcentration of zinc on a microcolumn of immobilized Alizarin Red S on alumina. The adsorbed analyte is then eluted with 250 µL of nitric acid (1 mol L-1 and is transported to flame atomic absorption spectrometer for quantification. The effect of pH, sample and eluent flow rates and presence of various cations and anions on the retention of zinc was investigated. The sorption of zinc was quantitative in the pH range of 5.5-8.5. For a sample volume of 25 mL an enrichment factor of 144 and a detection limit (3S of 0.2 µg L-1 was obtained. The precision (RSD, n=7 was 3.0% at the 20 µg L-1 level. The developed system was successfully applied to the determination of zinc in water samples, hair, urine and saliva.

  12. Metal-silica sol-gel materials

    Science.gov (United States)

    Stiegman, Albert E. (Inventor)

    2002-01-01

    The present invention relates to a single phase metal-silica sol-gel glass formed by the co-condensation of a transition metal with silicon atoms where the metal atoms are uniformly distributed within the sol-gel glass as individual metal centers. Any transition metal may be used in the sol-gel glasses. The present invention also relates to sensor materials where the sensor material is formed using the single phase metal-silica sol-gel glasses. The sensor materials may be in the form of a thin film or may be attached to an optical fiber. The present invention also relates to a method of sensing chemicals using the chemical sensors by monitoring the chromatic change of the metal-silica sol-gel glass when the chemical binds to the sensor. The present invention also relates to oxidation catalysts where a metal-silica sol-gel glass catalyzes the reaction. The present invention also relates to a method of performing oxidation reactions using the metal-silica sol-gel glasses. The present invention also relates to organopolymer metal-silica sol-gel composites where the pores of the metal-silica sol-gel glasses are filled with an organic polymer polymerized by the sol-gel glass.

  13. Facile alkylation of 4-nitrobenzotriazole and its platelet aggregation inhibitory activity.

    Science.gov (United States)

    Singh, Dhandeep; Silakari, Om

    2017-10-15

    We explored the facile alkylation of 4-nitrobenzotriazole under basic conditions and the synthesized derivatives were tested for their potential ADP induced platelet aggregation inhibition activity in comparison with standard drug ticagrelor (selective P2Y12 inhibitor). The nitro group at 4-position is highly activating toward alkylation reactions (under strong basic conditions) and resulted in formation of degradation product like 3-nitrobenzene-1,2-diamine which make isolation of alkyl products very difficult. We optimized the reaction under mild basic condition (potassium carbonate and DMF) which is devoid of any degradation product. This is perhaps the first report of 4-nitrobenzotriazole derivatives possessing platelet aggregation inhibitory activity. Generally activity increases with increase in length of alkyl chain and 1-alkyl positional isomers were found to be more potent than 2-alkyl isomers. The benzoyl derivative was found to be the most potent [compound 22; (4-Nitro-1H-benzotriazol-1-yl)(phenyl)methanone; IC 50 =0.65±0.10mM] which may be attributed to electronegative oxygen atom and aromatic ring. Benzyl derivatives [compound 20; 1-Benzyl-4-nitro-1H-benzotriazole; IC 50 =0.81±0.08mM, compound 21; 2-Benzyl-4-nitro-2H-benzotriazole; IC 50 =0.82±0.19mM] and sulfonyl derivative [compound 23; 1-[(4-Methylphenyl)sulfonyl]-4-nitro-1H-benzotriazole; IC 50 =0.82±0.19mM] are also found to be highly active. Furthermore, all compounds possess P2Y12 binding affinity as confirmed by VASP/P2Y12 phosphorylation assay. Copyright © 2017. Published by Elsevier Ltd.

  14. Synthesis of alkyl-ether glycerophospholipids in rat glomerular mesangial cells: evidence for alkyldihydroxyacetone phosphate synthase activity

    International Nuclear Information System (INIS)

    Zanglis, A.; Lianos, E.A.

    1987-01-01

    We studied the ability of rat glomerular mesangial cells and their microsomal fractions to incorporate 1-[ 14 C]hexadecanol to glycerophospholipids via an O-alkyl ether linkage and assessed the presence and activity of the required enzyme: alkyl-dihydroxy acetone phosphate synthase. Suspensions of cultured mesangial cells incorporated 1-[ 14 C]hexadecanol to the phosphatidyl ethanolamine and phosphatidyl choline lipid pools, via a bond resistant to acid and base hydrolysis. When cell homogenates or microsomal fractions were incubated with palmitoyl-DHAP and 1-[ 14 C]hexadecanol, alkyl-DHAP and 1-O-alkyl glycerol were formed (alkyl:hexadecyl). The activity of the enzyme responsible for the O-alkyl product formation was calculated to be 2.5 +/- 0.3 and 544 +/- 50 pmoles/min/mg protein for mesangial cell homogenates and mesangial cell microsomes, respectively. These observations provide evidence that mesangial cells may elaborate either linked lipid precursors de novo for the biosynthesis of O-alkyl glycerophospholipids

  15. ATM regulates 3-methylpurine-DNA glycosylase and promotes therapeutic resistance to alkylating agents.

    Science.gov (United States)

    Agnihotri, Sameer; Burrell, Kelly; Buczkowicz, Pawel; Remke, Marc; Golbourn, Brian; Chornenkyy, Yevgen; Gajadhar, Aaron; Fernandez, Nestor A; Clarke, Ian D; Barszczyk, Mark S; Pajovic, Sanja; Ternamian, Christian; Head, Renee; Sabha, Nesrin; Sobol, Robert W; Taylor, Michael D; Rutka, James T; Jones, Chris; Dirks, Peter B; Zadeh, Gelareh; Hawkins, Cynthia

    2014-10-01

    Alkylating agents are a first-line therapy for the treatment of several aggressive cancers, including pediatric glioblastoma, a lethal tumor in children. Unfortunately, many tumors are resistant to this therapy. We sought to identify ways of sensitizing tumor cells to alkylating agents while leaving normal cells unharmed, increasing therapeutic response while minimizing toxicity. Using an siRNA screen targeting over 240 DNA damage response genes, we identified novel sensitizers to alkylating agents. In particular, the base excision repair (BER) pathway, including 3-methylpurine-DNA glycosylase (MPG), as well as ataxia telangiectasia mutated (ATM), were identified in our screen. Interestingly, we identified MPG as a direct novel substrate of ATM. ATM-mediated phosphorylation of MPG was required for enhanced MPG function. Importantly, combined inhibition or loss of MPG and ATM resulted in increased alkylating agent-induced cytotoxicity in vitro and prolonged survival in vivo. The discovery of the ATM-MPG axis will lead to improved treatment of alkylating agent-resistant tumors. Inhibition of ATM and MPG-mediated BER cooperate to sensitize tumor cells to alkylating agents, impairing tumor growth in vitro and in vivo with no toxicity to normal cells, providing an ideal therapeutic window. ©2014 American Association for Cancer Research.

  16. Near Infrared Spectroscopic Identification of Alkyl Aromatic Esters and Phenyl Ketones

    Science.gov (United States)

    Nelyubov, D. V.; Vazhenin, D. A.; Kudriavtsev, A. A.; Buzolina, A. Yu.

    2018-03-01

    Bands characterizing the content of carbon atoms in alkyl (7177-7205 cm-1) and phenyl structural fragments (9175-9192 cm-1) in organic molecules were revealed by studying the near infrared spectra of such compounds. The optical density at the maxima of these absorption bands was shown to depend strongly on the fraction of carbon atoms in the corresponding fragments. The developed models proved to be adequate for determining the fraction of carbon atoms in alkyl aromatic esters and phenyl ketones. The feasibility of modeling the molecular structure of alkyl aromatic esters using regression models was demonstrated for the product of the condensation of oleic acid and benzyl alcohol.

  17. Resolving the chemical nature of nanodesigned silica surface obtained via a bottom-up approach.

    Science.gov (United States)

    Rahma, Hakim; Buffeteau, Thierry; Belin, Colette; Le Bourdon, Gwenaëlle; Degueil, Marie; Bennetau, Bernard; Vellutini, Luc; Heuzé, Karine

    2013-08-14

    The covalent grafting on silica surfaces of a functional dendritic organosilane coupling agent inserted, in a long alkyl chain monolayer, is described. In this paper, we show that depending on experimental parameters, particularly the solvent, it is possible to obtain a nanodesigned surface via a bottom-up approach. Thus, we succeed in the formation of both homogeneous dense monolayer and a heterogeneous dense monolayer, the latter being characterized by a nanosized volcano-type pattern (4-6 nm of height, 100 nm of width, and around 3 volcanos/μm(2)) randomly distributed over the surface. The dendritic attribute of the grafted silylated coupling agent affords enough anchoring sites to immobilize covalently functional gold nanoparticles (GNPs), coated with amino PEG polymer to resolve the chemical nature of the surfaces and especially the volcano type nanopattern structures of the heterogeneous monolayer. Thus, the versatile surface chemistry developed herein is particularly challenging as the nanodesign is straightforward achieved in a bottom-up approach without any specific lithography device.

  18. Silica aerogel Cerenkov counter

    International Nuclear Information System (INIS)

    Yasumi, S.; Masaike, A.; Yamamoto, A.; Yoshimura, Y.; Kawai, H.

    1984-03-01

    In order to obtain silica aerogel radiators of good quality, the prescription used by Saclay group has been developed. We have done several experiments using beams from KEK.PS to test the performance of a Cerenkov counter with aerogel modules produced in KEK. It turned out that these modules had excellent quality. The production rate of silica aerogel in KEK is 15 -- 20 litres a week. Silica aerogel modules of 20 x 10 x 3 cm 3 having the refractive index of 1.058 are successfully being used by Kyoto University group in the KEK experiment E92 (Σ). Methodes to produce silica aerogel with higher refractive index than 1.06 has been investigated both by heating an module with the refractive index of 1.06 and by hydrolyzing tetraethyl silicate. (author)

  19. Melt flow and mechanical properties of silica/perfluoropolymer nanocomposites Fabricated by direct melt-compounding without surface modification on nano-silica.

    Science.gov (United States)

    Tanahashi, Mitsuru; Watanabe, Yusuke; Lee, Jeong-Chang; Takeda, Kunihiko; Fujisawa, Toshiharu

    2009-01-01

    The authors have previously developed a novel method for the fabrication of silica/perfluoropolymer nanocomposites, wherein nano-sized silica particles without surface modification were dispersed uniformly through breakdown of loosely packed agglomerates of silica nanoparticles with low fracture strength in a polymer melt during direct melt-compounding. The method consists of two stages; the first stage involves preparation of the loose silica agglomerate, and the second stage involves melt-compounding of a completely hydrophobic perfluoropolymer, PFA (poly(tetrafluoroethylene-co-perfluoropropylvinylether)), with the loose silica agglomerates. By using this simple method without any lipophilic treatment of the silica surfaces, silica nanoparticles with a primary diameter of 190 nm could be dispersed uniformly into the PFA matrix. The main purpose of the present study is to evaluate the melt flow and tensile properties of silica/PFA nanocomposites fabricated by the above method. In order to elucidate the effects of the size of the dispersed silica in the PFA matrix on the properties of the composites, silica/PFA composite samples exhibiting the dispersion of larger-sized silica particle-clusters were fabricated as negative controls of the silica dispersion state. The results obtained under the present experimental conditions showed that the size of the dispersed silica in the PFA matrix exerts a strong influence on the ultimate tensile properties, such as tensile strength and elongation at break, and the melt flow rate (MFR) of the composite materials. The MFR of the silica/PFA nanocomposite became higher than that of the pure PFA without silica addition, although the MFR of the PFA composites containing larger silica particle-clusters became much lower than that of the pure PFA. Furthermore, uniform dispersion of isolated silica nanoparticles was found to improve not only the Young's modulus but also the ultimate tensile properties of the composite.

  20. Synthesis and evaluation of novel caged DNA alkylating agents bearing 3,4-epoxypiperidine structure.

    Science.gov (United States)

    Kawada, Yuji; Kodama, Tetsuya; Miyashita, Kazuyuki; Imanishi, Takeshi; Obika, Satoshi

    2012-07-14

    Previously, we reported that the 3,4-epoxypiperidine structure, whose design was based on the active site of DNA alkylating antitumor antibiotics, azinomycins A and B, possesses prominent DNA cleavage activity. In this report, novel caged DNA alkylating agents, which were designed to be activated by UV irradiation, were synthesized by the introduction of four photo-labile protecting groups to a 3,4-epoxypiperidine derivative. The DNA cleavage activity and cytotoxicity of the caged DNA alkylating agents were examined under UV irradiation. Four caged DNA alkylating agents showed various degrees of bioactivity depending on the photosensitivity of the protecting groups.

  1. Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

    International Nuclear Information System (INIS)

    Fujimura, T.; Hayakawa, N.; Kuriyama, I.

    1978-01-01

    The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

  2. Multifunctional nanomedicine with silica: Role of silica in nanoparticles for theranostic, imaging, and drug monitoring.

    Science.gov (United States)

    Chen, Fang; Hableel, Ghanim; Zhao, Eric Ruike; Jokerst, Jesse V

    2018-07-01

    The idea of multifunctional nanomedicine that enters the human body to diagnose and treat disease without major surgery is a long-standing dream of nanomaterials scientists. Nanomaterials show incredible properties that are not found in bulk materials, but achieving multi-functionality on a single material remains challenging. Integrating several types of materials at the nano-scale is critical to the success of multifunctional nanomedicine device. Here, we describe the advantages of silica nanoparticles as a tool for multifunctional nano-devices. Silica nanoparticles have been intensively studied in drug delivery due to their biocompatibility, degradability, tunable morphology, and ease of modification. Moreover, silica nanoparticles can be integrated with other materials to obtain more features and achieve theranostic capabilities and multimodality for imaging applications. In this review, we will first compare the properties of silica nanoparticles with other well-known nanomaterials for bio-applications and describe typical routes to synthesize and integrate silica nanoparticles. We will then highlight theranostic and multimodal imaging application that use silica-based nanoparticles with a particular interest in real-time monitoring of therapeutic molecules. Finally, we will present the challenges and perspective on future work with silica-based nanoparticles in medicine. Copyright © 2018 Elsevier Inc. All rights reserved.

  3. N- and C-alkylation of seven-membered iminosugars generates potent glucocerebrosidase inhibitors and F508del-CFTR correctors.

    Science.gov (United States)

    Désiré, J; Mondon, M; Fontelle, N; Nakagawa, S; Hirokami, Y; Adachi, I; Iwaki, R; Fleet, G W J; Alonzi, D S; Twigg, G; Butters, T D; Bertrand, J; Cendret, V; Becq, F; Norez, C; Marrot, J; Kato, A; Blériot, Y

    2014-11-28

    The glycosidase inhibitory properties of synthetic C-alkyl and N-alkyl six-membered iminosugars have been extensively studied leading to therapeutic candidates. The related seven-membered iminocyclitols have been less examined despite the report of promising structures. Using an in house ring enlargement/C-alkylation as well as cross-metathesis methodologies as the key steps, we have undertaken the synthesis and biological evaluation of a library of fourteen 2C- and eight N-alkyl tetrahydroxylated azepanes starting from an easily available glucopyranose-derived azidolactol. Four, six, nine and twelve carbon atom alkyl chains have been introduced. The study of two distinct D-gluco and L-ido stereochemistries for the tetrol pattern as well as R and S configurations for the C-2 carbon bearing the C-alkyl chain is reported. We observed that C-alkylation of the L-ido tetrahydroxylated azepane converts it from an α-L-fucosidase to a β-glucosidase and β-galactosidase inhibitor while N-alkylation of the D-gluco iminosugar significantly improves its inhibition profile leading to potent β-glucosidase, β-galactosidase, α-L-rhamnosidase and β-glucuronidase inhibitors whatever the stereochemistry of the alkyl chain. Interestingly, the N-alkyl chain length usually parallels the azepane inhibitor potency as exemplified by the identification of a potent glucocerebrosidase inhibitor (Ki 1 μM) bearing a twelve carbon atom chain. Additionally, several C-alkyl azepanes demonstrated promising F508del-CFTR correction unlike the parent tetrahydroxyazepanes. None of the C-alkyl and N-alkyl azepanes did inhibit ER α-glucosidases I or II.

  4. Coupling sequential injection on-line preconcentration by means of a renewable microcolumn with ion-exchange beads with detection by electrothermal atomic absorption spectrometry. Comparing the performance of eluting the loaded beads with transporting them directly into the graphite tube

    DEFF Research Database (Denmark)

    Wang, Jianhua; Hansen, Elo Harald

    2001-01-01

    The design of a flow injection/sequential injection (FIA/SIA) on-line preconcentration system incorporating a renewable microcolumn with ion-exchange beads and interfaced with an electrothermal atomic absorption spectrometry (ETAAS) detector is described, and its practical applicability.......4% for the procedure in which the loaded beads are transported directly to the graphite furnace for pyrolysis and atomization, and even improved in comparison to the traditional unidirectional and bidirectional repetitive elution procedures which under comparable conditions yield R.S.D.-values of 5.8 and 4...

  5. One-step formation of bifunctionnal aryl/alkyl grafted films on conducting surfaces by the reduction of diazonium salts in the presence of alkyl iodides.

    Science.gov (United States)

    Hetemi, Dardan; Hazimeh, Hassan; Decorse, Philippe; Galtayries, Anouk; Combellas, Catherine; Kanoufi, Frédéric; Pinson, Jean; Podvorica, Fetah I

    2015-05-19

    The formation of partial perfluoroalkyl or alkyl radicals from partial perfluoroalkyl or alkyl iodides (ICH2CH2C6F13 and IC6H13) and their reaction with surfaces takes place at low driving force (∼-0.5 V/SCE) when the electrochemical reaction is performed in acetonitrile in the presence of diazonium salts (ArN2(+)), at a potential where the latter is reduced. By comparison to the direct grafting of ICH2CH2C6F13, this corresponds to a gain of ∼2.1 V in the case of 4-nitrobenzenediazonium. Such electrochemical reaction permits the modification of gold surfaces (and also carbon, iron, and copper) with mixed aryl-alkyl groups (Ar = 3-CH3-C6H4, 4-NO2-C6H4, and 4-Br-C6H4, R = C6H13 or (CH2)2-C6F13). These strongly bonded mixed layers are characterized by IRRAS, XPS, ToF-SIMS, ellipsometry, water contact angles, and cyclic voltammetry. The relative proportions of grafted aryl and alkyl groups can be varied along with the relative concentrations of diazonium and iodide components in the grafting solution. The formation of the films is assigned to the reaction of aryl and alkyl radicals on the surface and on the first grafted layer. The former is obtained from the electrochemical reduction of the diazonium salt; the latter results from the abstraction of an iodine atom by the aryl radical. The mechanism involved in the growth of the film provides an example of complex surface radical chemistry.

  6. Study of the pluronic-silica interaction in synthesis of mesoporous silica under mild acidic conditions.

    Science.gov (United States)

    Sundblom, Andreas; Palmqvist, Anders E C; Holmberg, Krister

    2010-02-02

    The interaction between silica and poly(ethylene oxide) (PEO) in water may appear trivial and it is generally stated that hydrogen bonding is responsible for the attraction. However, a literature search shows that there is not a consensus with respect to the mechanism behind the attractive interaction. Several papers claim that only hydrogen bonding is not sufficient to explain the binding. The silica-PEO interaction is interesting from an academic perspective and it is also exploited in the preparation of mesoporous silica, a material of considerable current interest. This study concerns the very early stage of synthesis of mesoporous silica under mild acidic conditions, pH 2-5, and the aim is to shed light on the interaction between silica and the PEO-containing structure directing agent. The synthesis comprises two steps. An organic silica source, tetraethylorthosilicate (TEOS), is first hydrolyzed and Pluronic P123, a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer, is subsequently added at different time periods following the hydrolysis of TEOS. It is shown that the interaction between the silica and the Pluronic is dependent both on the temperature and on the time between onset of TEOS hydrolysis and addition of the copolymer. The results show that the interaction is mainly driven by entropy. The effect of the synthesis temperature and of the time between hydrolysis and addition of the copolymer on the final material is also studied. The material with the highest degree of mesoorder was obtained when the reaction was performed at 20 degrees C and the copolymer was added 40 h after the start of TEOS hydrolysis. It is claimed that the reason for the good ordering of the silica is that whereas particle formation under these conditions is fast, the rate of silica condensation is relatively low.

  7. Silica coatings on clarithromycin.

    Science.gov (United States)

    Bele, Marjan; Dmitrasinovic, Dorde; Planinsek, Odon; Salobir, Mateja; Srcic, Stane; Gaberscek, Miran; Jamnik, Janko

    2005-03-03

    Pre-crystallized clarithromycin (6-O-methylerythromycin A) particles were coated with silica from the tetraethyl orthosilicate (TEOS)-ethanol-aqueous ammonia system. The coatings had a typical thickness of 100-150 nm and presented about 15 wt.% of the silica-drug composite material. The properties of the coatings depended on reactant concentration, temperature and mixing rate and, in particular, on the presence of a cationic surfactant (cetylpyridinium chloride). In the presence of cetylpyridinium chloride the silica coatings slightly decreased the rate of pure clarithromycin dissolution.

  8. Oxygen configurations in silica

    International Nuclear Information System (INIS)

    Chelikowsky, James R.; Chadi, D. J.; Binggeli, N.

    2000-01-01

    We propose a transition state for oxygen in silica. This state is produced by the insertion of an oxygen molecule into the Si-O-Si bond, i.e., it consists of producing a Si-O-O-O-Si bond. This state allows molecular oxygen diffusion in silica without breaking the molecular O 2 bond and it is energetically more stable than a peroxy configuration. This configuration may allow for exchange of molecular oxygen with the oxygen in the silica framework. (c) 2000 The American Physical Society

  9. The Effect of Various Acids to the Gelation Process to the Silica Gel Characteristic Using Organic Silica

    Science.gov (United States)

    Rahman, NA; Widiyastuti, W.; Sigit, D.; Ajiza, M.; Sujana, W.

    2018-01-01

    Bagasse ash is solid waste of cane sugar industry which contain of silica more than 51%. Some previous study of silica gel from bagasse ash have been conducted often and been applied. This study concerns about the effect of various acid used in the process of gelation to the characteristic of silica gel produced. Then, this silica gel will be used as adsorbent. As that, the silica gel must fulfill the requirements of adsorbent, as have good pores characteristics, fit in mesoporous size so that adsorbent diffusion process is not disturbed. A fitted pores size of silica gel can be prepared by managing acid concentration used. The effect of acid, organic acid (tartaric acid) and inorganic acid (hydrochloric acid), is investigated in detail. The acid is added into sodium silicate solution in that the gel is formed, the pores structures can be investigated with BET, the crystal form is analyzed with XRD and the pore structure is analyzed visually with SEM. By managing the acid concentration added, it gets the effect of acid to the pore structure of silica gel. The bigger concentration is, the bigger the pore’s size of silica gel produced.

  10. Production of high-octane, unleaded motor fuel by alkylation of isobutane with isoamylenes obtained by dehydrogenation of isopentane

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, T. Jr.; Hann, P.D.

    1981-01-31

    A process combination, with inter-cooperation, for producing high-octane alkylates comprising (a) dehydrogenating isopentane to isopentenes (amylenes), (b) introducing the mixture of said amylenes and unconverted isopentane into an HF alkylation unit for reaction with fresh or recycled isobutane, (c) separating the alkylation products into high octane alkylates, isopentane (for recycling to the dehydrogenation reactor) and isobutane (for recycling to the alkylation reactor).

  11. Highly Effective Gene Transfection In Vivo by Alkylated Polyethylenimine

    Directory of Open Access Journals (Sweden)

    Jennifer A. Fortune

    2011-01-01

    Full Text Available We mechanistically explored the effect of increased hydrophobicity of the polycation on the efficacy and specificity of gene delivery in mice. N-Alkylated linear PEIs with varying alkyl chain lengths and extent of substitution were synthesized and characterized by biophysical methods. Their in vivo transfection efficiency, specificity, and biodistribution were investigated. N-Ethylation improves the in vivo efficacy of gene expression in the mouse lung 26-fold relative to the parent polycation and more than quadruples the ratio of expression in the lung to that in all other organs. N-Propyl-PEI was the best performer in the liver and heart (581- and 3.5-fold enhancements, resp. while N-octyl-PEI improved expression in the kidneys over the parent polymer 221-fold. As these enhancements in gene expression occur without changing the plasmid biodistribution, alkylation does not alter the cellular uptake but rather enhances transfection subsequent to cellular uptake.

  12. Benign and efficient preparation of thioethers by solvent-free S-alkylation of thiols with alkyl halides catalyzed by potassium fluoride on alumina

    DEFF Research Database (Denmark)

    Nguyen, Kha Ngoc; Duus, Fritz; Luu, Thi Xuan Thi

    2016-01-01

    The preparation of thioethers by S-alkylation of various thiols with alkyl halides under solvent-free reaction conditions using potassium fluoride on alumina (KF/Al2O3) as a solid catalyst has been investigated in detail with respect to three different modes of reaction activation (ultrasound...... irradiation, microwave irradiation, and conventional heating) for obtaining maximum yield of the thioether. The importance of KF/Al2O3 as a particularly efficient catalyst was corroborated for all three modes of reaction activation, although the reaction time was found to be strongly dependent on the mode...

  13. Characterization of reaction conditions providing rapid and specific cysteine alkylation for peptide-based mass spectrometry.

    Science.gov (United States)

    Paulech, Jana; Solis, Nestor; Cordwell, Stuart J

    2013-01-01

    Alkylation converts Cys thiols to thioethers and prevents unwanted side reactions, thus facilitating mass spectrometric identification of Cys-containing peptides. Alkylation occurs preferentially at Cys due to its high nucleophilicity, however reactions at other such sites are possible. N-ethylmaleimide (NEM) shows rapid reaction kinetics with Cys and careful definition of reaction conditions results in little reactivity at other sites. Analysis of a protein standard alkylated under differing reaction conditions (pH, NEM concentrations and reaction times) was performed using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) and selected reaction monitoring (SRM) of NEM-modified and unmodified peptide pairs. Mis-alkylation sites at primary and secondary amines were identified and limited to one equivalent of NEM. No evidence for hydroxyl or thioether alkylation was observed. Improved specificity was achieved by restricting the pH below neutral, NEM concentration below 10mM and/or reaction time to below 5min. Maximal removal of Cys activity was observed in tissue homogenates at 40mM NEM within 1min, dependent upon efficient protein denaturation. SRM assays identified peptide-specific levels of mis-alkylation, indicating that NEM-modified to unmodified ratios did not exceed 10%, with the exception of Cys alkylation that proceeded to 100%, and some Lys residues that resulted in tryptic missed cleavages. High reactivity was observed for His residues considering their relatively low abundance. These data indicate that rapid and specific Cys alkylation is possible with NEM under relatively mild conditions, with more abrasive conditions leading to increased non-specific alkylation without appreciable benefit for MS-based proteomics. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. Dependence of micelle size and shape on detergent alkyl chain length and head group.

    Directory of Open Access Journals (Sweden)

    Ryan C Oliver

    Full Text Available Micelle-forming detergents provide an amphipathic environment that can mimic lipid bilayers and are important tools for solubilizing membrane proteins for functional and structural investigations in vitro. However, the formation of a soluble protein-detergent complex (PDC currently relies on empirical screening of detergents, and a stable and functional PDC is often not obtained. To provide a foundation for systematic comparisons between the properties of the detergent micelle and the resulting PDC, a comprehensive set of detergents commonly used for membrane protein studies are systematically investigated. Using small-angle X-ray scattering (SAXS, micelle shapes and sizes are determined for phosphocholines with 10, 12, and 14 alkyl carbons, glucosides with 8, 9, and 10 alkyl carbons, maltosides with 8, 10, and 12 alkyl carbons, and lysophosphatidyl glycerols with 14 and 16 alkyl carbons. The SAXS profiles are well described by two-component ellipsoid models, with an electron rich outer shell corresponding to the detergent head groups and a less electron dense hydrophobic core composed of the alkyl chains. The minor axis of the elliptical micelle core from these models is constrained by the length of the alkyl chain, and increases by 1.2-1.5 Å per carbon addition to the alkyl chain. The major elliptical axis also increases with chain length; however, the ellipticity remains approximately constant for each detergent series. In addition, the aggregation number of these detergents increases by ∼16 monomers per micelle for each alkyl carbon added. The data provide a comprehensive view of the determinants of micelle shape and size and provide a baseline for correlating micelle properties with protein-detergent interactions.

  15. Study on the Alkylation Reactions of N(7)-Unsubstituted 1,3-Diazaoxindoles.

    Science.gov (United States)

    Kókai, Eszter; Halász, Judit; Dancsó, András; Nagy, József; Simig, Gyula; Volk, Balázs

    2017-05-19

    The chemistry of the 5,7-dihydro-6 H -pyrrolo[2,3- d ]pyrimidin-6-one (1,3-diazaoxindole) compound family, possessing a drug-like scaffold, is unexplored. In this study, the alkylation reactions of N (7)-unsubstituted 5-isopropyl-1,3-diazaoxindoles bearing various substituents at the C (2) position have been investigated. The starting compounds were synthesized from the C (5)-unsubstituted parent compounds by condensation with acetone and subsequent catalytic reduction of the 5-isopropylidene moiety. Alkylation of the thus obtained 5-isopropyl derivatives with methyl iodide or benzyl bromide in the presence of a large excess of sodium hydroxide led to 5,7-disubstituted derivatives. Use of butyllithium as the base rendered alkylation in the C (5) position possible with reasonable selectivity, without affecting the N (7) atom. During the study on the alkylation reactions, some interesting by-products were also isolated and characterized.

  16. Masked N-Heterocyclic Carbene-Catalyzed Alkylation of Phenols with Organic Carbonates.

    Science.gov (United States)

    Lui, Matthew Y; Yuen, Alexander K L; Masters, Anthony F; Maschmeyer, Thomas

    2016-09-08

    An easily prepared masked N-heterocyclic carbene, 1,3-dimethylimidazolium-2-carboxylate (DMI-CO2 ), was investigated as a "green" and inexpensive organocatalyst for the alkylation of phenols. The process made use of various low-toxicity and renewable alkylating agents, such as dimethyl- and diethyl carbonate, in a focused microwave reactor. DMI-CO2 was found to be a very active catalyst and excellent yields of a range of aryl alkyl ethers were obtained under relatively benign conditions. The observed difference in the conversion behavior of phenol methylation, in the presence of either the carbene or 1,8-diazabicycloundec-7-ene (DBU) catalyst, was rationalized on the basis of mechanistic investigations. The primary mode of action for the N-heterocyclic carbene is nucleophilic catalysis. Activation of the dialkyl carbonate electrophile results in concomitant evolution of an organo-soluble alkoxide, which deprotonates the phenolic starting material. In contrast, DBU is initially protonated by the phenol and thus consumed. Subsequent regeneration and participation in nucleophilic catalysis only becomes significant after some phenolate alkylation occurs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Determination of alkylation of bacterial DNA as a rapid test for toxicological evaluation of alkylating xenobiotic agents

    Energy Technology Data Exchange (ETDEWEB)

    Botzenhart, K.; Waldner-Sander, S.; Schweinsberg, F.

    1986-05-01

    Alkylated purine bases from hydrolized DNA can be separated by HPLC and quantified with a fluorescence detector. We applied this method to bacterial DNA. 7-methylguanine was detected after treatment of Serratia marcescens with iodoacetamide, dimethyl sulfate and with polluted air.

  18. Preparation and characterization of hybrid Nafion/silica and Nafion/silica/PTA membranes for redox flow batteries

    Energy Technology Data Exchange (ETDEWEB)

    Glibin, V.; Pupkevich, V.; Svirko, L.; Karamanev, D. [Western Ontario Univ., London, ON (Canada). Dept. of Biochemical and Chemical Engineering

    2008-07-01

    Redox flow batteries are both efficient and cost-effective. However, the long-term stability of most ion-exchange membranes is limited as a result of the high oxidation rates of ions with high redox potentials. A method of synthesizing multi-component Nafion-silica and Nafion-silica-PTA membranes was presented in this study, which also investigated the electrochemical and ion transport properties of the membranes. Membranes were cast from dimethylformamide (DMFA) solution. The iron ion diffusion kinetics of the Nafion-silica and Nafion-silica PTA membranes were studied by dialysis. Results of the investigation demonstrated that the introduction of silica and phosphotungstic acid (PTA) into the Nafion membrane composition resulted in a significant decrease of ion transfer through the membrane. The addition of PTA also increased membrane permeability to ferric ions. The low iron diffusion coefficient and high ionic conductivity of the Nafion-silica membrane makes it a promising material for use in redox flow batteries. 4 refs., 1 tab., 1 fig.

  19. Cytotoxic geranylated xanthones and O-alkylated derivatives of alpha-mangostin

    DEFF Research Database (Denmark)

    Ha, Ly Dieu; Hansen, Poul Erik; Vang, Ole

    2009-01-01

    Two new geranylated xanthones, 6-O-methylcowanin (4) and oliverixanthone (5), along with five known compounds, cowanin, rubraxanthone, cowaxanthone, cowanol, and β-mangostin, have been isolated from the bark of Garcinia oliveri. For comparison of their biological activities, one mono- and seven di-O-alkylated...... that α-mangostin had the strongest activity, and all the O-alkylated α-mangostin derivatives showed reduced activity compared to the naturally occurring α-mangostin....

  20. Depolymerization of coal by oxidation and alkylation; Sanka bunkai to alkyl ka ni yoru sekitan kaijugo

    Energy Technology Data Exchange (ETDEWEB)

    Tomita, H.; Isoda, T.; Kusakabe, K.; Morooka, S. [Kyushu University, Fukuoka (Japan). Faculty of Engineering; Hayashi, J. [Hokkaido University, Sapporo (Japan). Center for Advanced Research of Energy Technology

    1996-10-28

    Change in depolymerization degree and coal structure was studied for depolymerization treatment of coal in various alcohol containing aqueous hydrogen peroxide. In experiment, the mixture of Yallourn coal, alcohol and aqueous hydrogen peroxide was agitated in nitrogen atmosphere of normal pressure at 70{degree}C for 12 hours. As the experimental result, the methanol solubility of only 5% of raw coal increased up to 35.2% by hydrogen peroxide treatment, while the yield of insoluble matters also decreased from 94% to 62%. Most of the gas produced during treatment was composed of inorganic gases such as CO and CO2, and its carbon loss was extremely decreased by adding alcohol. From the analytical result of carbon loss in hydrogen peroxide treatment, it was clarified that alkylation advances with introduction of alkyl group derived from alcohol into coal by hydrogen peroxide treatment under a coexistence of alcohol, and depolymerization reaction of coal itself is thus promoted by alcohol. 4 refs., 7 figs., 1 tab.

  1. Kinetic study of the anaerobic biodegradation of alkyl polyglucosides and the influence of their structural parameters.

    Science.gov (United States)

    Ríos, Francisco; Fernández-Arteaga, Alejandro; Lechuga, Manuela; Jurado, Encarnación; Fernández-Serrano, Mercedes

    2016-05-01

    This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L(-1), are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment.

  2. Silica-Coated Liposomes for Insulin Delivery

    Directory of Open Access Journals (Sweden)

    Neelam Dwivedi

    2010-01-01

    Full Text Available Liposomes coated with silica were explored as protein delivery vehicles for their enhanced stability and improved encapsulation efficiency. Insulin was encapsulated within the fluidic phosphatidylcholine lipid vesicles by thin film hydration at pH 2.5, and layer of silica was formed above lipid bilayer by acid catalysis. The presence of silica coating and encapsulated insulin was identified using confocal and electron microscopy. The native state of insulin present in the formulation was evident from Confocal Micro-Raman spectroscopy. Silica coat enhances the stability of insulin-loaded delivery vehicles. In vivo study shows that these silica coated formulations were biologically active in reducing glucose levels.

  3. Recent developments in isobutane/olefin alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Lercher, J.A.; Feller, A. [Inst. fuer Technische Chemie, Technische Univ. Muenchen (Germany)

    2002-07-01

    The isobutane/alkene alkylation is reviewed with respect to recent process developments based on liquid and solid acid catalysts. A brief overview about the established processes is given followed by the description of new processes based on solid acids under development. (orig.)

  4. Mechanism of the extraction of nitric acid and water by organic solutions of tertiary alkyl-amines

    International Nuclear Information System (INIS)

    Gourisse, D.

    1966-06-01

    The micellar aggregation of tri-alkyl-ammonium nitrates in low polarity organic solvents has been verified by viscosity, conductivity and sedimentation velocity measurements. The aggregation depends upon the polarity of solvent, the length of the alkyl radicals and the organic concentration of the various constituents (tri-alkyl-ammonium nitrate, tri-alkyl-amine, nitric acid, water). The amine salification law has been established and the excess nitric acid and water solubilities in the organic solutions have been measured. Nitric acid and water are slightly more soluble in micellar organic solutions than in molecular organic solutions. A description of excess nitric acid containing tri-alkyl-ammonium nitrate solutions is proposed. (author) [fr

  5. Radioiodination of proteins by reductive alkylation

    International Nuclear Information System (INIS)

    Panuska, J.R.; Parker, C.W.

    1987-01-01

    The use of the aliphatic aldehyde, para-hydroxyphenylacetaldehyde as the reactive moiety in the radioiodination of proteins by reductive alkylation is described. The para-hydroxyphenyl group is radiolabeled with 125 I, reacted through its aliphatic aldehyde group with primary amino groups on proteins to form a reversible Schiff base linkage which can then be stabilized with the mild reducing agent NaCNBH 3 . The introduction of the methylene group between the benzene ring and the aldehyde group increases its reactivity with protein amino groups permitting efficient labeling at low aldehyde concentrations. Using this method, radioiodinated proteins with high specific activity can be produced. The reductive alkylation procedure is advantageous in that the labeling conditions are mild, the reaction is specific for lysyl residues, and the modification of the epsilon-ammonium group of lysine results in ionizable secondary amino groups avoiding major changes in protein charge

  6. Silica artificial opal incorporated with silver nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Li Wenjiang, E-mail: wjli@zju.edu.cn [Center for Optical and Electromagnetic Research, State Key Laboratory for Modern Optical Instrumentation, Zhejiang University, Joint Research Center of Photonics of the Royal Institute of Technology and Zhejiang University, Zijingang Campus, Room 210, East Building 5, Hangzhou 310058 (China); Sun Tan [Center for Optical and Electromagnetic Research, State Key Laboratory for Modern Optical Instrumentation, Zhejiang University, Joint Research Center of Photonics of the Royal Institute of Technology and Zhejiang University, Zijingang Campus, Room 210, East Building 5, Hangzhou 310058 (China)

    2009-07-15

    The silica artificial opal with a three-dimensional (3D) periodic structure was prepared using highly monodispersed silica microspheres by a force packing method in ITO glass cell. The silica artificial opal incorporated with silver nanoparticles was fabricated by the electroplating technique. The optical microscope images of the synthetic sample and the corresponding optical properties were measured after each treatment of electroplating-washing-drying circle. The transmission and reflection spectra presented a red shift, showing that the effective refractive index of the complex silver/silica opal increased after each electroplating. Combining the SEM images, it was seen that the silver nanoparticles could be directly deposited on the surface of silica spheres in the opaline structure. The silver/silica complex opal film could provide a simple way to tune the opal properties by controlling silver nanoparticles in the silica opal. The silver/silica opal crystal structures could be used for nano-photonic circuits, white-light LEDs or as photocatalysts.

  7. Silica artificial opal incorporated with silver nanoparticles

    International Nuclear Information System (INIS)

    Li Wenjiang; Sun Tan

    2009-01-01

    The silica artificial opal with a three-dimensional (3D) periodic structure was prepared using highly monodispersed silica microspheres by a force packing method in ITO glass cell. The silica artificial opal incorporated with silver nanoparticles was fabricated by the electroplating technique. The optical microscope images of the synthetic sample and the corresponding optical properties were measured after each treatment of electroplating-washing-drying circle. The transmission and reflection spectra presented a red shift, showing that the effective refractive index of the complex silver/silica opal increased after each electroplating. Combining the SEM images, it was seen that the silver nanoparticles could be directly deposited on the surface of silica spheres in the opaline structure. The silver/silica complex opal film could provide a simple way to tune the opal properties by controlling silver nanoparticles in the silica opal. The silver/silica opal crystal structures could be used for nano-photonic circuits, white-light LEDs or as photocatalysts.

  8. Silica nanoparticle stability in biological media revisited.

    Science.gov (United States)

    Yang, Seon-Ah; Choi, Sungmoon; Jeon, Seon Mi; Yu, Junhua

    2018-01-09

    The stability of silica nanostructure in the core-silica shell nanomaterials is critical to understanding the activity of these nanomaterials since the exposure of core materials due to the poor stability of silica may cause misinterpretation of experiments, but unfortunately reports on the stability of silica have been inconsistent. Here, we show that luminescent silver nanodots (AgNDs) can be used to monitor the stability of silica nanostructures. Though relatively stable in water and phosphate buffered saline, silica nanoparticles are eroded by biological media, leading to the exposure of AgNDs from AgND@SiO 2 nanoparticles and the quenching of nanodot luminescence. Our results reveal that a synergistic effect of organic compounds, particularly the amino groups, accelerates the erosion. Our work indicates that silica nanostructures are vulnerable to cellular medium and it may be possible to tune the release of drug molecules from silica-based drug delivery vehicles through controlled erosion.

  9. Thermally stable silica-coated hydrophobic gold nanoparticles.

    Science.gov (United States)

    Kanehara, Masayuki; Watanabe, Yuka; Teranishi, Toshiharu

    2009-01-01

    We have successfully developed a method for silica coating on hydrophobic dodecanethiol-protected Au nanoparticles with coating thickness ranging from 10 to 40 nm. The formation of silica-coated Au nanoparticles could be accomplished via the preparation of hydrophilic Au nanoparticle micelles by cationic surfactant encapsulation in aqueous phase, followed by hydrolysis of tetraethylorthosilicate on the hydrophilic surface of gold nanoparticle micelles. Silica-coated Au nanoparticles exhibited quite high thermal stability, that is, no agglomeration of the Au cores could be observed after annealing at 600 degrees C for 30 min. Silica-coated Au nanoparticles could serve as a template to derive hollow nanoparticles. An addition of NaCN solution to silica-coated Au nanoparticles led the formation of hollow silica nanoparticles, which were redispersible in deionized water. The formation of the hollow silica nanoparticles results from the mesoporous structures of the silica shell and such a mesoporous structure is applicable to both catalyst support and drug delivery.

  10. Targeting the plasma membrane of neoplastic cells through alkylation: a novel approach to cancer chemotherapy.

    Science.gov (United States)

    Trendowski, Matthew; Fondy, Thomas P

    2015-08-01

    Although DNA-directed alkylating agents and related compounds have been a mainstay in chemotherapeutic protocols due to their ability to readily interfere with the rapid mitotic progression of malignant cells, their clinical utility is limited by DNA repair mechanisms and immunosuppression. However, the same destructive nature of alkylation can be reciprocated at the cell surface using novel plasma membrane alkylating agents. Plasma membrane alkylating agents have elicited long term survival in mammalian models challenged with carcinomas, sarcomas, and leukemias. Further, a specialized group of plasma membrane alkylating agents known as tetra-O-acetate haloacetamido carbohydrate analogs (Tet-OAHCs) potentiates a substantial leukocyte influx at the administration and primary tumor site, indicative of a potent immune response. The effects of plasma membrane alkylating agents may be further potentiated through the use of another novel class of chemotherapeutic agents, known as dihydroxyacetone phosphate (DHAP) inhibitors, since many cancer types are known to rely on the DHAP pathway for lipid synthesis. Despite these compelling data, preliminary clinical trials for plasma membrane-directed agents have yet to be considered. Therefore, this review is intended for academics and clinicians to postulate a novel approach of chemotherapy; altering critical malignant cell signaling at the plasma membrane surface through alkylation, thereby inducing irreversible changes to functions needed for cell survival.

  11. Iminium ion chemistry of mitosene DNA alkylating agents. Enriched 13C NMR and isolation studies.

    Science.gov (United States)

    Ouyang, A; Skibo, E B

    2000-05-16

    Described herein is a study of the reductive alkylation chemistry of mitosene antitumor agents. We employed a 13C-enriched electrophilic center to probe the fate of the iminium ion resulting from reductive activation. The 13C-labeled center permitted the identification of complex products resulting from alkylation reactions. In the case of DNA reductive alkylation, the type and number of alkylation sites were readily assessed by 13C NMR. Although there has been much excellent work done in the area of mitosene chemistry and biochemistry, the present study provides a number of new findings: (1) The major fate of the iminium ion is head-to-tail polymerization, even in dilute solutions. (2) Dithionite reductive activation results in the formation of mitosene sulfite esters as well as the previously observed sulfonate adducts. (3) The mitosene iminium ion alkylates the adenosine 6-amino group as well as the guanosine 2-amino group. The identification of the latter adduct was greatly facilitated by the 13C-label at the electrophilic center. (4) The mitosene iminium ion alkylates DNA at both nitrogen and oxygen centers without any apparent base selectivity. The complexity of mitosene reductive alkylation of DNA will require continued adduct isolation studies.

  12. Aag-initiated base excision repair drives alkylation-induced retinal degeneration in mice.

    Science.gov (United States)

    Meira, Lisiane B; Moroski-Erkul, Catherine A; Green, Stephanie L; Calvo, Jennifer A; Bronson, Roderick T; Shah, Dharini; Samson, Leona D

    2009-01-20

    Vision loss affects >3 million Americans and many more people worldwide. Although predisposing genes have been identified their link to known environmental factors is unclear. In wild-type animals DNA alkylating agents induce photoreceptor apoptosis and severe retinal degeneration. Alkylation-induced retinal degeneration is totally suppressed in the absence of the DNA repair protein alkyladenine DNA glycosylase (Aag) in both differentiating and postmitotic retinas. Moreover, transgenic expression of Aag activity restores the alkylation sensitivity of photoreceptors in Aag null animals. Aag heterozygotes display an intermediate level of retinal degeneration, demonstrating haploinsufficiency and underscoring that Aag expression confers a dominant retinal degeneration phenotype.

  13. Stimulatory and protective effects of alkylating agents applied in ultra-low concentrations.

    Science.gov (United States)

    Pukhalsky, A L; Shmarina, G V

    2001-01-01

    Alkylating drugs belonging to the nitrogen mustard family are known as cytostatic and immunosuppressive agents. Ultra-low doses of these drugs may demonstrate pharmacological effects unlike this category of drugs. In the case of a gradual dose decrease, the number of targets for alkylation is also reduced and the drug switches from cytostatic to cell growth modifier. We postulate that application of ultra-low doses of alkylating drugs may result in a beneficial effect in the therapy of diseases associated with chronic inflammation of the mucosa, especially with the signs of epithelial atrophy. Copyright 2001 S. Karger AG, Basel

  14. Neurotoxicity induced by alkyl nitrites: Impairment in learning/memory and motor coordination.

    Science.gov (United States)

    Cha, Hye Jin; Kim, Yun Ji; Jeon, Seo Young; Kim, Young-Hoon; Shin, Jisoon; Yun, Jaesuk; Han, Kyoungmoon; Park, Hye-Kyung; Kim, Hyung Soo

    2016-04-21

    Although alkyl nitrites are used as recreational drugs, there is only little research data regarding their effects on the central nervous system including their neurotoxicity. This study investigated the neurotoxicity of three representative alkyl nitrites (isobutyl nitrite, isoamyl nitrite, and butyl nitrite), and whether it affected learning/memory function and motor coordination in rodents. Morris water maze test was performed in mice after administrating the mice with varying doses of the substances in two different injection schedules of memory acquisition and memory retention. A rota-rod test was then performed in rats. All tested alkyl nitrites lowered the rodents' capacity for learning and memory, as assessed by both the acquisition and retention tests. The results of the rota-rod test showed that isobutyl nitrite in particular impaired motor coordination in chronically treated rats. The mice chronically injected with isoamyl nitrite also showed impaired function, while butyl nitrite had no significant effect. The results of the water maze test suggest that alkyl nitrites may impair learning and memory. Additionally, isoamyl nitrite affected the rodents' motor coordination ability. Collectively, our findings suggest that alkyl nitrites may induce neurotoxicity, especially on the aspect of learning and memory function. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  15. Design of novel antitumor DNA alkylating agents: the benzacronycine series.

    Science.gov (United States)

    David-Cordonnier, Marie-Hélène; Laine, William; Gaslonde, Thomas; Michel, Sylvie; Tillequin, Francois; Koch, Michel; Léonce, Stéphane; Pierré, Alain; Bailly, Christian

    2004-03-01

    Acronycine, a natural alkaloid originally extracted from the bark of the Australian ash scrub Acronychia baueri, has shown a significant antitumor activity in animal models. Acronycine has been tested against human cancers in the early 1980s, but the clinical trials showed modest therapeutic effects and its development was rapidly discontinued. In order to optimize the antineoplastic effect, different benzoacronycine derivatives were synthesized. Among those, the di-acetate compound S23906-1 was recently identified as a promising anticancer drug candidate and a novel alkylating agent specifically reacting with the exocylic 2-NH2 group of guanines in DNA. The study of DNA bonding capacity of acronycine derivatives leads to the identification of the structural requirements for DNA alkylation. In nearly all cases, the potent alkylating agents, such as S23906-1, were found to be much more cytotoxic than the unreactive analogs such as acronycine itself or diol derivatives. Alkylation of DNA by the monoacetate derivative S28687-1, which is a highly reactive hydrolysis metabolite of S23906-1, occurs with a marked preference for the N2 position of guanine. Other bionucleophiles can react with S23906-1. The benzacronycine derivatives, which efficiently alkylate DNA, also covalently bind to the tripeptide glutathione (GSH) but not to the oxidized product glutathione disulfide. Here we review the reactivity of S23906-1 and some derivatives toward DNA and GSH. The structure-activity relationships in the benzacronycine series validate the reaction mechanism implicating DNA as the main molecular target. S23906-1 stands as the most promising lead of a medicinal chemistry program aimed at discovering novel antitumor drugs based on the acronycine skeleton.

  16. Chitosan-silica complex membranes from sulfonic acid functionalized silica nanoparticles for pervaporation dehydration of ethanol-water solutions.

    Science.gov (United States)

    Liu, Ying-Ling; Hsu, Chih-Yuan; Su, Yu-Huei; Lai, Juin-Yih

    2005-01-01

    Nanosized silica particles with sulfonic acid groups (ST-GPE-S) were utilized as a cross-linker for chitosan to form a chitosan-silica complex membranes, which were applied to pervaporation dehydration of ethanol-water solutions. ST-GPE-S was obtained from reacting nanoscale silica particles with glycidyl phenyl ether, and subsequent sulfonation onto the attached phenyl groups. The chemical structure of the functionalized silica was characterized with FTIR, (1)H NMR, and energy-dispersive X-ray. Homogeneous dispersion of the silica particles in chitosan was observed with electronic microscopies, and the membranes obtained were considered as nanocomposites. The silica nanoparticles in the membranes served as spacers for polymer chains to provide extra space for water permeation, so as to bring high permeation rates to the complex membranes. With addition of 5 parts per hundred of functionalized silica into chitosan, the resulting membrane exhibited a separation factor of 919 and permeation flux of 410 g/(m(2) h) in pervaporation dehydration of 90 wt % ethanol aqueous solution at 70 degrees C.

  17. Chemotherapy-induced pulmonary hypertension: role of alkylating agents.

    Science.gov (United States)

    Ranchoux, Benoît; Günther, Sven; Quarck, Rozenn; Chaumais, Marie-Camille; Dorfmüller, Peter; Antigny, Fabrice; Dumas, Sébastien J; Raymond, Nicolas; Lau, Edmund; Savale, Laurent; Jaïs, Xavier; Sitbon, Olivier; Simonneau, Gérald; Stenmark, Kurt; Cohen-Kaminsky, Sylvia; Humbert, Marc; Montani, David; Perros, Frédéric

    2015-02-01

    Pulmonary veno-occlusive disease (PVOD) is an uncommon form of pulmonary hypertension (PH) characterized by progressive obstruction of small pulmonary veins and a dismal prognosis. Limited case series have reported a possible association between different chemotherapeutic agents and PVOD. We evaluated the relationship between chemotherapeutic agents and PVOD. Cases of chemotherapy-induced PVOD from the French PH network and literature were reviewed. Consequences of chemotherapy exposure on the pulmonary vasculature and hemodynamics were investigated in three different animal models (mouse, rat, and rabbit). Thirty-seven cases of chemotherapy-associated PVOD were identified in the French PH network and systematic literature analysis. Exposure to alkylating agents was observed in 83.8% of cases, mostly represented by cyclophosphamide (43.2%). In three different animal models, cyclophosphamide was able to induce PH on the basis of hemodynamic, morphological, and biological parameters. In these models, histopathological assessment confirmed significant pulmonary venous involvement highly suggestive of PVOD. Together, clinical data and animal models demonstrated a plausible cause-effect relationship between alkylating agents and PVOD. Clinicians should be aware of this uncommon, but severe, pulmonary vascular complication of alkylating agents. Copyright © 2015 American Society for Investigative Pathology. Published by Elsevier Inc. All rights reserved.

  18. Sequence selectivity of azinomycin B in DNA alkylation and cross-linking: a QM/MM study.

    Science.gov (United States)

    Senthilnathan, Dhurairajan; Kalaiselvan, Anbarasan; Venuvanalingam, Ponnambalam

    2013-01-01

    Azinomycin B--a well-known antitumor drug--forms cross-links with DNA through alkylation of purine bases and blocks tumor cell growth. This reaction has been modeled using the ONIOM (B3LYP/6-31+g(d):UFF) method to understand the mechanism and sequence selectivity. ONIOM results have been checked for reliability by comparing them with full quantum mechanics calculations for selected paths. Calculations reveal that, among the purine bases, guanine is more reactive and is alkylated by aziridine ring through the C10 position, followed by alkylation of the epoxide ring through the C21 position of Azinomycin B. While the mono alkylation is controlled kinetically, bis-alkylation is controlled thermodynamically. Solvent effects were included using polarized-continuum-model calculations and no significant change from gas phase results was observed.

  19. Isobutane/butene alkylation on solid catalysts. Where do we stand?

    Energy Technology Data Exchange (ETDEWEB)

    Weitkamp, J.; Traa, Y. [Institute of Chemical Technology I, University of Stuttgart, D-70550 Stuttgart (Germany)

    1999-02-24

    Liquid-phase processes with concentrated sulfuric acid or hydrogen fluoride as catalysts are currently being used in petroleum refining for the manufacture of alkylation gasoline from isobutane and butenes. While the product, i.e., alkylate, is a most valuable gasoline component, the existing processes for its manufacture are less satisfactory. Replacement of the liquid catalysts by a solid acid is an important target of modern research. In the past two decades, a large number of solid acids have been scrutinized, and at least four developments were driven till the pilot plant stage. In this paper, an attempt is made to rationalize, on a mechanistic basis, the selectivity loss almost always encountered with solid acids after relatively short times-on-stream. Suggestions are made concerning a more target-oriented research on isobutane/alkene alkylation in the future

  20. Polypyrrole Doped with Alkyl Benzene Sulphonates

    DEFF Research Database (Denmark)

    Bay, Lasse; Mogensen, Naja; Skaarup, Steen

    2002-01-01

    The properties of polypyrrole (PPy) are to a large extent determined by the condition of synthesis and especially by the counterion incorporated as dopant during synthesis. In this work, PPy doped with different alkyl benzenesulfonates are compared. The polymer films are prepared by constant curr...

  1. Amorphous silica from rice husk at various temperatures

    International Nuclear Information System (INIS)

    Javed, S.J.; Feroze, N.; Tajwar, S.

    2008-01-01

    Rice husk is being used as a source of energy in many heat generating system because of its high calorific value and its availability in many rice producing areas. Rice husk contains approximately 20% silica which is presented in hydrated form. This hydrated silica can be retrieved as amorphous silica under controlled thermal conditions. Uncontrolled burning of rice husk produces crystalline silica which is not reactive silica but can be used as filler in many applications. Amorphous silica is reactive silica which has better market value due to its reactive nature in process industry. The present study deals with the production of amorphous silica at various temperatures from rice husk. Various ashes were prepared in tube furnace by changing the burning temperatures for fixed time intervals and analyzed by XRD. It has been observed that for two hours calculation's of rice husk renders mostly amorphous silica at 650 degree C where as at higher temperatures crystalline silica was obtained. (author)

  2. Elementary steps and reaction pathways in the aqueous phase alkylation of phenol with ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Eckstein, Sebastian; Hintermeier, Peter H.; Olarte, Mariefel V.; Liu, Yue; Baráth, Eszter; Lercher, Johannes A.

    2017-08-01

    The hydronium ion normalized reaction rate in aqueous phase alkylation of phenol with ethanol on H-MFI zeolites increases with decreasing concentration of acid sites. Higher rates are caused by higher concentrations of phenol in the zeolite pores, as the concentration of hydronium ions generated by zeolite Brønsted acid sites decreases. Considering the different concentrations of reacting species it is shown that the intrinsic rate constant for alkylation is independent of the concentration of hydronium ions in the zeolite pores. Alkylation at the aromatic ring of phenol and of toluene as well as O-alkylation of phenol have the same activation energy, 104 ± 5 kJ/mol. This is energetic barrier to form the ethyl carbenium ion from ethanol associated to the hydronium ion. Thus, in both the reaction pathways the catalyst involves a carbenium ion, which forms a bond to a nucleophilic oxygen (ether formation) or carbon (alkylation).

  3. Cellular membrane trafficking of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Fang, I-Ju [Iowa State Univ., Ames, IA (United States)

    2012-01-01

    This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulf some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine

  4. Synthesis of Various Silica Nanoparticles for Foam Stability

    International Nuclear Information System (INIS)

    Yoon, Suk Bon; Yoon, Inho; Jung, Chonghun; Kim, Chorong; Choi, Wangkyu; Moon, Jeikwon

    2013-01-01

    The synthesis of the non-porous silica nanoparticles with uniform sizes has been reported through the Sto ber method, the synthesis of meso porous silica nanoparticles with a specific morphology such as core-shell, rod-like, and hexagonal shapes is not so common. As a synthetic strategy for controlling the particle size, shape, and porosity, the synthesis of core-shell silicas with meso porous shells formed on silica particle cores through the self-assembly of silica precursor and organic templates or spherical meso porous silicas using modified Sto ber method was also reported. Recently, in an effort to reduce the amount of radioactive waste and enhance the decontamination efficiency during the decontamination process of nuclear facilities contaminated with radionuclides, a few research for the preparation of the decontamination foam containing solid nanoparticles has been reported. In this work, the silica nanoparticles with various sizes, shapes, and structures were synthesized based on the previous literatures. The resulting silica nanoparticles were used to investigate the effect of the nanoparticles on the foam stability. In a study on the foam stability using various silica nanoparticles, the results showed that the foam volume and liquid volume in foam was enhanced when using a smaller size and lower density of the silica nanoparticles. Silica nanoparticles with various sizes, shapes, and structures such as a non-porous, meso porous core-shell, and meso porous silica were synthesized to investigate the effect of the foam stability. The sizes and structural properties of the silica nanoparticles were easily controlled by varying the amount of silica precursor, surfactant, and ammonia solution as a basic catalyst. The foam prepared using various silica nanoparticles showed that foam the volume and liquid volume in the foam were enhanced when using a smaller size and lower density of the silica nanoparticles

  5. Comparison of the reactivity of alkyl and alkyl amine precursors with native oxide GaAs(100) and InAs(100) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Henegar, A.J., E-mail: henegar1@umbc.edu; Gougousi, T., E-mail: gougousi@umbc.edu

    2016-12-30

    Graphical abstract: The interaction of the native oxides of GaAs(100) and InAs(100) with alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition (ALD) of Al{sub 2}O{sub 3} and TiO{sub 2} is compared. Al{sub 2}O{sub 3} if found to be a significantly better barrier against the transport of the surface native oxide during the film deposition as well as after post-deposition heat treatment. This superior blocking ability also limits the removal of the native oxides during the Al{sub 2}O{sub 3} ALD process. - Highlights: • Native oxide diffusion is required for continuous native oxide removal. • The diffusion barrier capabilities of Al{sub 2}O{sub 3} limits native oxide removal during ALD. • Arsenic oxide exhibits higher mobility from InAs compared to GaAs substrates. • Oxygen scavenging from the surface by trimethyl aluminum is confirmed. - Abstract: In this manuscript we compare the interaction of alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition with III-V native oxides. For that purpose we deposit Al{sub 2}O{sub 3} and TiO{sub 2}, using H{sub 2}O as the oxidizer, on GaAs(100) and InAs(100) native oxide surfaces. We find that there are distinct differences in the behavior of the two films. For the Al{sub 2}O{sub 3} ALD very little native oxide removal happens after the first few ALD cycles while the interaction of the alkyl amine precursor for TiO{sub 2} and the native oxides continues well after the surface has been covered with 2 nm of TiO{sub 2}. This difference is traced to the superior properties of Al{sub 2}O{sub 3} as a diffusion barrier. Differences are also found in the behavior of the arsenic oxides of the InAs and GaAs substrates. The arsenic oxides from the InAs surface are found to mix more efficiently in the growing dielectric film than those from the GaAs surface. This difference is attributed to

  6. Comparison of the reactivity of alkyl and alkyl amine precursors with native oxide GaAs(100) and InAs(100) surfaces

    International Nuclear Information System (INIS)

    Henegar, A.J.; Gougousi, T.

    2016-01-01

    Graphical abstract: The interaction of the native oxides of GaAs(100) and InAs(100) with alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition (ALD) of Al_2O_3 and TiO_2 is compared. Al_2O_3 if found to be a significantly better barrier against the transport of the surface native oxide during the film deposition as well as after post-deposition heat treatment. This superior blocking ability also limits the removal of the native oxides during the Al_2O_3 ALD process. - Highlights: • Native oxide diffusion is required for continuous native oxide removal. • The diffusion barrier capabilities of Al_2O_3 limits native oxide removal during ALD. • Arsenic oxide exhibits higher mobility from InAs compared to GaAs substrates. • Oxygen scavenging from the surface by trimethyl aluminum is confirmed. - Abstract: In this manuscript we compare the interaction of alkyl (trimethyl aluminum) and alkyl amine (tetrakis dimethylamino titanium) precursors during thermal atomic layer deposition with III-V native oxides. For that purpose we deposit Al_2O_3 and TiO_2, using H_2O as the oxidizer, on GaAs(100) and InAs(100) native oxide surfaces. We find that there are distinct differences in the behavior of the two films. For the Al_2O_3 ALD very little native oxide removal happens after the first few ALD cycles while the interaction of the alkyl amine precursor for TiO_2 and the native oxides continues well after the surface has been covered with 2 nm of TiO_2. This difference is traced to the superior properties of Al_2O_3 as a diffusion barrier. Differences are also found in the behavior of the arsenic oxides of the InAs and GaAs substrates. The arsenic oxides from the InAs surface are found to mix more efficiently in the growing dielectric film than those from the GaAs surface. This difference is attributed to lower native oxide stability as well as an initial diffusion path formation by the indium oxides.

  7. Silica removal in industrial effluents with high silica content and low hardness.

    Science.gov (United States)

    Latour, Isabel; Miranda, Ruben; Blanco, Angeles

    2014-01-01

    High silica content of de-inked paper mill effluents is limiting their regeneration and reuse after membrane treatments such as reverse osmosis (RO). Silica removal during softening processes is a common treatment; however, the effluent from the paper mill studied has a low hardness content, which makes the addition of magnesium compounds necessary to increase silica removal. Two soluble magnesium compounds (MgCl₂∙6H₂O and MgSO₄∙7H₂O) were tested at five dosages (250-1,500 mg/L) and different initial pH values. High removal rates (80-90%) were obtained with both products at the highest pH tested (11.5). With these removal efficiencies, it is possible to work at high RO recoveries (75-85%) without silica scaling. Although pH regulation significantly increased the conductivity of the waters (at pH 11.5 from 2.1 to 3.7-4.0 mS/cm), this could be partially solved by using Ca(OH)₂ instead of NaOH as pH regulator (final conductivity around 3.0 mS/cm). Maximum chemical oxygen demand (COD) removal obtained with caustic soda was lower than with lime (15 vs. 30%). Additionally, the combined use of a polyaluminum coagulant during the softening process was studied; the coagulant, however, did not significantly improve silica removal, obtaining a maximum increase of only 10%.

  8. Structure-function relationships governing activity and stability of a DNA alkylation damage repair thermostable protein.

    Science.gov (United States)

    Perugino, Giuseppe; Miggiano, Riccardo; Serpe, Mario; Vettone, Antonella; Valenti, Anna; Lahiri, Samarpita; Rossi, Franca; Rossi, Mosè; Rizzi, Menico; Ciaramella, Maria

    2015-10-15

    Alkylated DNA-protein alkyltransferases repair alkylated DNA bases, which are among the most common DNA lesions, and are evolutionary conserved, from prokaryotes to higher eukaryotes. The human ortholog, hAGT, is involved in resistance to alkylating chemotherapy drugs. We report here on the alkylated DNA-protein alkyltransferase, SsOGT, from an archaeal species living at high temperature, a condition that enhances the harmful effect of DNA alkylation. The exceptionally high stability of SsOGT gave us the unique opportunity to perform structural and biochemical analysis of a protein of this class in its post-reaction form. This analysis, along with those performed on SsOGT in its ligand-free and DNA-bound forms, provides insights in the structure-function relationships of the protein before, during and after DNA repair, suggesting a molecular basis for DNA recognition, catalytic activity and protein post-reaction fate, and giving hints on the mechanism of alkylation-induced inactivation of this class of proteins. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  9. Hydride Transfer versus Deprotonation Kinetics in the Isobutane–Propene Alkylation Reaction: A Computational Study

    OpenAIRE

    Liu, Chong; van Santen, Rutger A.; Poursaeidesfahani, Ali; Vlugt, Thijs J. H.; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2017-01-01

    The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate o...

  10. Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-fluoro)thiophenes

    KAUST Repository

    Fei, Zhuping

    2015-06-03

    © 2015 American Chemical Society. We report two strategies toward the synthesis of 3-alkyl-4-fluorothiophenes containing straight (hexyl and octyl) and branched (2-ethylhexyl) alkyl groups. We demonstrate that treatment of the dibrominated monomer with 1 equiv of alkyl Grignard reagent leads to the formation of a single regioisomer as a result of the pronounced directing effect of the fluorine group. Polymerization of the resulting species affords highly regioregular poly(3-alkyl-4-fluoro)thiophenes. Comparison of their properties to those of the analogous non-fluorinated polymers shows that backbone fluorination leads to an increase in the polymer ionization potential without a significant change in optical band gap. Fluorination also results in an enhanced tendency to aggregate in solution, which is ascribed to a more co-planar backbone on the basis of Raman and DFT calculations. Average charge carrier mobilities in field-effect transistors are found to increase by up to a factor of 5 for the fluorinated polymers.

  11. 21 CFR 176.120 - Alkyl ketene dimers.

    Science.gov (United States)

    2010-04-01

    ..., processing, preparing, treating, packaging, transporting, or holding food, subject to the provisions of this... paperboard. (c) The alkyl ketene dimers may be used in the form of an aqueous emulsion which may contain...

  12. Effect of alkyl length of cationic surfactants on desorption of Cs from contaminated clay

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Bo Hyun; Park, Chan Woo; Yang, Hee Man; Seo, Bum Kyoung; Lee, Kune Woo [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Park, So Jin [Chungnam National University, Daejeon (Korea, Republic of)

    2017-03-15

    In this study, desorption characteristics of Cs from clay according to the hydrophobic alkyl chain length of the cationic surfactant were investigated. Alkyltrimethylammonium bromide was used as a cationic surfactant, and the length of the hydrophobic alkyl chain of the cationic surfactant was varied from –octyl to –cetyl. The adsorbed amount of the cationic surfactant on montmorillonite increased with the length of the hydrophobic alkyl chain, and intercalation of the cationic surfactant into the clay interlayer increased the interlayer distances. The Cs removal efficiency was also enhanced with increasing alkyl chain length, and the cationic surfactant with the cetyl group showed a maximum Cs removal efficiency of 99±2.9%.

  13. Nearest neighbor affects G:C to A:T transitions induced by alkylating agents.

    OpenAIRE

    Glickman, B W; Horsfall, M J; Gordon, A J; Burns, P A

    1987-01-01

    The influence of local DNA sequence on the distribution of G:C to A:T transitions induced in the lacI gene of E. coli by a series of alkylating agents has been analyzed. In the case of nitrosoguanidine, two nitrosoureas and a nitrosamine, a strong preference for mutation at sites proceeded 5' by a purine base was noted. This preference was observed with both methyl and ethyl donors where the predicted common ultimate alkylating species is the alkyl diazonium ion. In contrast, this preference ...

  14. 46 CFR 151.50-86 - Alkyl (C7-C9) nitrates.

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Alkyl (C7-C9) nitrates. 151.50-86 Section 151.50-86... CARRYING BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-86 Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to...

  15. Stereoselective Alkylation of Thiacalix[4]arenes

    Czech Academy of Sciences Publication Activity Database

    Himl, M.; Pojarová, M.; Stibor, I.; Sýkora, Jan; Lhoták, P.

    2005-01-01

    Roč. 46, č. 3 (2005), s. 461-464 ISSN 0040-4039 R&D Projects: GA ČR(CZ) GA104/00/1722 Institutional research plan: CEZ:AV0Z40720504 Keywords : calixarene * alkylation * conformations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.477, year: 2005

  16. hf alkylation in the 1980's: the role of isobutane/olefin ratio

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, T. Jr.

    1978-08-01

    Research devoted to maximizing no-lead octane numbers in motor fuel is reported. Results of the studies are the basis for the following conclusions: 1. Isobutane alkylate made from either propylene, butene-2, or C/sub 3/--C/sub 4/ mixed olefins is a low sensitivity, high motor octane product. Typically, C/sub 3/--C/sub 4/ mixed olefin alkylate has a clear motor octane number of about 92.2 and a clear Research octane number of about 93.5. 2. In separate studies with propylene, butene-2 and C/sub 3/--C/sub 4/ mixed olefins, increasing the isobutane-to-olefin ratio suppressed the formation of high molecular weight residue, indicating a substantial reduction in the role of olefin polymerization to large ions. The overall result of increasing ratio was an improvement in selectivity to high-octane components in the alkylate. 3. When alkylating isobutane with propylene, increasing the ratio resulted in a decrease in the concentration of C/sub 7/-fraction (primary product) and an increase in the C/sub 8/-fraction (from chain initiation and subsequent hydrogen transfer). At the same time, the production of chain-termination-product propane also increased. 4. When alkylating isobutane with C/sub 3/--C/sub 4/ mixed olefins, increasing the ratio showed the same trend obtained in separate alkylation tests with propylene and butene-2. As the ratio increased, the concentration of C/sub 7/-fraction (primary propylene--isobutane product) decreased and the concentration of C/sub 8/-fraction increased markedly. Thus, increasing isobutane-to-olefin ratio exerted a strong effect on alkylate quality in the area of about 5 to 1 to 20 to 1; this effect diminished at ratios 20:1.

  17. Building blocks for ionic liquids: Vapor pressures and vaporization enthalpies of 1-(n-alkyl)-imidazoles

    International Nuclear Information System (INIS)

    Emel'yanenko, Vladimir N.; Portnova, Svetlana V.; Verevkin, Sergey P.; Skrzypczak, Andrzej; Schubert, Thomas

    2011-01-01

    Highlights: → We measured vapor pressures of the 1-(n-alkyl)-imidazoles by transpiration method. → Variations on the alkyl chain length n were C 3 , C 5 -C 7 , and C 9 -C 10 . → Enthalpies of vaporization were derived from (p, T) dependencies. → Enthalpies of vaporization at 298.15 K were linear dependent on the chain length. - Abstract: Vapor pressures of the linear 1-(n-alkyl)-imidazoles with the alkyl chain C 3 , C 5 -C 7 , and C 9 -C 10 have been measured by the transpiration method. The molar enthalpies of vaporization Δ l g H m of these compounds were derived from the temperature dependencies of vapor pressures. A linear correlation of enthalpies of vaporization Δ l g H m (298.15 K) of the 1-(n-alkyl)-imidazoles with the chain length has been found.

  18. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage is most likely achieved by ligand participation which could involve......-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation...... an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

  19. Effects of Photo-chemically Activated Alkylating Agents of the FR900482 Family on Chromatin

    OpenAIRE

    Subramanian, Vidya; Ducept, Pascal; Williams, Robert M.; Luger, Karolin

    2007-01-01

    Bioreductive alkylating agents are an important class of clinical antitumor antibiotics that cross-link and mono-alkylate DNA. Here we use a synthetic photochemically activated derivative of FR400482 to investigate the molecular mechanism of this class of drugs in a biologically relevant context. We find that the organization of DNA into nucleosomes effectively protects it against drug-mediated cross-linking, while permitting mono-alkylation. This modification has the potential to form covale...

  20. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu

    2013-05-17

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  1. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu; Zhu, Bo; Lee, Richmond; Yang, Wenguo; Tan, Davin; Yang, Caiyun; Han, Zhiqiang; Yan, Lin; Huang, Kuo-Wei; Jiang, Zhiyong

    2013-01-01

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  2. The Pozzolanic reaction of silica fume

    DEFF Research Database (Denmark)

    Jensen, Ole Mejlhede

    2012-01-01

    Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone. In the ......Silica fume is a very important supplementary cementitious binder in High-Performance and Ultra High-Performance Concretes. Through its pozzolanic reaction the silica fume densifies the concrete micro-structure, in particular it strengthens the paste-aggregate interfacial transition zone....... In the present paper different aspects of the pozzolanic reaction of silica fume are investigated. These include chemical shrinkage, isothermal heat development and strength development. Key data for these are given and compared with theoretical calculations, and based on presented measurements the energy...

  3. Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols.

    Science.gov (United States)

    Li, Junjun; Liu, Yuxuan; Tang, Weijun; Xue, Dong; Li, Chaoqun; Xiao, Jianliang; Wang, Chao

    2017-10-17

    The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. DNA Damage Induced by Alkylating Agents and Repair Pathways

    Science.gov (United States)

    Kondo, Natsuko; Takahashi, Akihisa; Ono, Koji; Ohnishi, Takeo

    2010-01-01

    The cytotoxic effects of alkylating agents are strongly attenuated by cellular DNA repair processes, necessitating a clear understanding of the repair mechanisms. Simple methylating agents form adducts at N- and O-atoms. N-methylations are removed by base excision repair, AlkB homologues, or nucleotide excision repair (NER). O6-methylguanine (MeG), which can eventually become cytotoxic and mutagenic, is repaired by O6-methylguanine-DNA methyltransferase, and O6MeG:T mispairs are recognized by the mismatch repair system (MMR). MMR cannot repair the O6MeG/T mispairs, which eventually lead to double-strand breaks. Bifunctional alkylating agents form interstrand cross-links (ICLs) which are more complex and highly cytotoxic. ICLs are repaired by complex of NER factors (e.g., endnuclease xeroderma pigmentosum complementation group F-excision repair cross-complementing rodent repair deficiency complementation group 1), Fanconi anemia repair, and homologous recombination. A detailed understanding of how cells cope with DNA damage caused by alkylating agents is therefore potentially useful in clinical medicine. PMID:21113301

  5. 21 CFR 584.700 - Hydrophobic silicas.

    Science.gov (United States)

    2010-04-01

    ...) Product. Amorphous fumed hydrophobic silica or precipitated hydrophobic silica (CAS Reg. No. 68611-0944... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Hydrophobic silicas. 584.700 Section 584.700 Food... DRUGS, FEEDS, AND RELATED PRODUCTS FOOD SUBSTANCES AFFIRMED AS GENERALLY RECOGNIZED AS SAFE IN FEED AND...

  6. Biomimetic silica encapsultation of living cells

    Science.gov (United States)

    Jaroch, David Benjamin

    Living cells perform complex chemical processes on size and time scales that artificial systems cannot match. Cells respond dynamically to their environment, acting as biological sensors, factories, and drug delivery devices. To facilitate the use of living systems in engineered constructs, we have developed several new approaches to create stable protective microenvironments by forming bioinspired cell-membrane-specific silica-based encapsulants. These include vapor phase deposition of silica gels, use of endogenous membrane proteins and polysaccharides as a site for silica nucleation and polycondensation in a saturated environment, and protein templated ordered silica shell formation. We demonstrate silica layer formation at the surface of pluripotent stem-like cells, bacterial biofilms, and primary murine and human pancreatic islets. Materials are characterized by AFM, SEM and EDS. Viability assays confirm cell survival, and metabolite flux measurements demonstrate normal function and no major diffusion limitations. Real time PCR mRNA analysis indicates encapsulated islets express normal levels of genetic markers for β-cells and insulin production. The silica glass encapsulant produces a secondary bone like calcium phosphate mineral layer upon exposure to media. Such bioactive materials can improve device integration with surrounding tissue upon implantation. Given the favorable insulin response, bioactivity, and long-term viability observed in silica-coated islets, we are currently testing the encapsulant's ability to prevent immune system recognition of foreign transplants for the treatment of diabetes. Such hybrid silica-cellular constructs have a wide range of industrial, environmental, and medical applications.

  7. Structural Characterization of N-Alkylated Twisted Amides: Consequences for Amide Bond Resonance and N-C Cleavage.

    Science.gov (United States)

    Hu, Feng; Lalancette, Roger; Szostak, Michal

    2016-04-11

    Herein, we describe the first structural characterization of N-alkylated twisted amides prepared directly by N-alkylation of the corresponding non-planar lactams. This study provides the first experimental evidence that N-alkylation results in a dramatic increase of non-planarity around the amide N-C(O) bond. Moreover, we report a rare example of a molecular wire supported by the same amide C=O-Ag bonds. Reactivity studies demonstrate rapid nucleophilic addition to the N-C(O) moiety of N-alkylated amides, indicating the lack of n(N) to π*(C=O) conjugation. Most crucially, we demonstrate that N-alkylation activates the otherwise unreactive amide bond towards σ N-C cleavage by switchable coordination. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. A new parameter-free soft-core potential for silica and its application to simulation of silica anomalies

    Energy Technology Data Exchange (ETDEWEB)

    Izvekov, Sergei, E-mail: sergiy.izvyekov.civ@mail.mil; Rice, Betsy M. [Weapons and Materials Research Directorate, U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005 (United States)

    2015-12-28

    A core-softening of the effective interaction between oxygen atoms in water and silica systems and its role in developing anomalous thermodynamic, transport, and structural properties have been extensively debated. For silica, the progress with addressing these issues has been hampered by a lack of effective interaction models with explicit core-softening. In this work, we present an extension of a two-body soft-core interatomic force field for silica recently reported by us [S. Izvekov and B. M. Rice, J. Chem. Phys. 136(13), 134508 (2012)] to include three-body forces. Similar to two-body interaction terms, the three-body terms are derived using parameter-free force-matching of the interactions from ab initio MD simulations of liquid silica. The derived shape of the O–Si–O three-body potential term affirms the existence of repulsion softening between oxygen atoms at short separations. The new model shows a good performance in simulating liquid, amorphous, and crystalline silica. By comparing the soft-core model and a similar model with the soft-core suppressed, we demonstrate that the topology reorganization within the local tetrahedral network and the O–O core-softening are two competitive mechanisms responsible for anomalous thermodynamic and kinetic behaviors observed in liquid and amorphous silica. The studied anomalies include the temperature of density maximum locus and anomalous diffusivity in liquid silica, and irreversible densification of amorphous silica. We show that the O–O core-softened interaction enhances the observed anomalies primarily through two mechanisms: facilitating the defect driven structural rearrangements of the silica tetrahedral network and modifying the tetrahedral ordering induced interactions toward multiple characteristic scales, the feature which underlies the thermodynamic anomalies.

  9. Quantum molecular modeling of the interaction between guanine and alkylating agents--2--nitrogen mustard.

    Science.gov (United States)

    Hamza, A; Broch, H; Vasilescu, D

    1996-06-01

    The alkylation mechanism of guanine by nitrogen mustard (HN2) was studied by using a supermolecular modeling at the ab initio 6-31G level. Our computations show that interaction of guanine with the aziridinium form of HN2 necessitates a transition state for the N7 alkylation route. The pathway of N7-guanine alkylation by nitrogen and sulfur mustards is discussed on the basis of the Molecular Electrostatic Potential and HOMO-LUMO properties of these molecules.

  10. Microporous Silica Based Membranes for Desalination

    Directory of Open Access Journals (Sweden)

    João C. Diniz da Costa

    2012-09-01

    Full Text Available This review provides a global overview of microporous silica based membranes for desalination via pervaporation with a focus on membrane synthesis and processing, transport mechanisms and current state of the art membrane performance. Most importantly, the recent development and novel concepts for improving the hydro-stability and separating performance of silica membranes for desalination are critically examined. Research into silica based membranes for desalination has focussed on three primary methods for improving the hydro-stability. These include incorporating carbon templates into the microporous silica both as surfactants and hybrid organic-inorganic structures and incorporation of metal oxide nanoparticles into the silica matrix. The literature examined identified that only metal oxide silica membranes have demonstrated high salt rejections under a variety of feed concentrations, reasonable fluxes and unaltered performance over long-term operation. As this is an embryonic field of research several target areas for researchers were discussed including further improvement of the membrane materials, but also regarding the necessity of integrating waste or solar heat sources into the final process design to ensure cost competitiveness with conventional reverse osmosis processes.

  11. Charge properties and bacterial contact-killing of hyperbranched polyurea-polyethyleneimine coatings with various degrees of alkylation

    International Nuclear Information System (INIS)

    Roest, Steven; Mei, Henny C. van der; Loontjens, Ton J.A.; Busscher, Henk J.

    2015-01-01

    Highlights: • Cationic charge density does not reflect bacterial contact-killing by QUAT coatings. • Charge carrier and density reflect bacterial killing by QUAT coatings. • Fluorescein staining cannot distinguish charge carriers in cationic coatings. • Charge carrier and density of QUAT coatings are reflected in the N401.3 eV XPS peak. • The at.% N401.3 eV should be more than 0.45% for effective bacterial contact-killing. - Abstract: Coatings of immobilized-quaternary-ammonium-ions (QUAT) uniquely kill adhering bacteria upon contact. QUAT-coatings require a minimal cationic-charge surface density for effective contact-killing of adhering bacteria of around 10 14 cm −2 . Quaternization of nitrogen is generally achieved through alkylation. Here, we investigate the contribution of additional alkylation with methyl-iodide to the cationic-charge density of hexyl-bromide alkylated, hyperbranched polyurea-polyethyleneimine coatings measuring charge density with fluorescein staining. X-ray-photoelectron-spectroscopy was used to determine the at.% alkylated-nitrogen. Also streaming potentials, water contact-angles and bacterial contact-killing were measured. Cationic-charge density increased with methyl-iodide alkylation times up to 18 h, accompanied by an increase in the at.% alkylated-nitrogen. Zeta-potentials became more negative upon alkylation as a result of shielding of cationiccharges by hydrophobic alkyl-chains. Contact-killing of Gram-positive Staphylococci only occurred when the cationic-charge density exceeded 10 16 cm −2 and was carried by alkylated-nitrogen (electron-binding energy 401.3 eV). Gram-negative Escherichia coli was not killed upon contact with the coatings. There with this study reveals that cationic-charge density is neither appropriate nor sufficient to determine the ability of QUAT-coatings to kill adhering bacteria. Alternatively, the at.% of alkylated-nitrogen at 401.3 eV is proposed, as it reflects both cationic-charge and its

  12. Charge properties and bacterial contact-killing of hyperbranched polyurea-polyethyleneimine coatings with various degrees of alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Roest, Steven [University of Groningen, University Medical Center Groningen, Department of Biomedical Engineering, AntoniusDeusinglaan 1, 9713 AV Groningen (Netherlands); Mei, Henny C. van der, E-mail: h.c.van.der.mei@umcg.nl [University of Groningen, University Medical Center Groningen, Department of Biomedical Engineering, AntoniusDeusinglaan 1, 9713 AV Groningen (Netherlands); Loontjens, Ton J.A. [University of Groningen, Zernike Institute for Advanced Materials, Department of Polymer Chemistry, Nijenborgh 4, 9747 AG Groningen (Netherlands); Busscher, Henk J. [University of Groningen, University Medical Center Groningen, Department of Biomedical Engineering, AntoniusDeusinglaan 1, 9713 AV Groningen (Netherlands)

    2015-11-30

    Highlights: • Cationic charge density does not reflect bacterial contact-killing by QUAT coatings. • Charge carrier and density reflect bacterial killing by QUAT coatings. • Fluorescein staining cannot distinguish charge carriers in cationic coatings. • Charge carrier and density of QUAT coatings are reflected in the N401.3 eV XPS peak. • The at.% N401.3 eV should be more than 0.45% for effective bacterial contact-killing. - Abstract: Coatings of immobilized-quaternary-ammonium-ions (QUAT) uniquely kill adhering bacteria upon contact. QUAT-coatings require a minimal cationic-charge surface density for effective contact-killing of adhering bacteria of around 10{sup 14} cm{sup −2}. Quaternization of nitrogen is generally achieved through alkylation. Here, we investigate the contribution of additional alkylation with methyl-iodide to the cationic-charge density of hexyl-bromide alkylated, hyperbranched polyurea-polyethyleneimine coatings measuring charge density with fluorescein staining. X-ray-photoelectron-spectroscopy was used to determine the at.% alkylated-nitrogen. Also streaming potentials, water contact-angles and bacterial contact-killing were measured. Cationic-charge density increased with methyl-iodide alkylation times up to 18 h, accompanied by an increase in the at.% alkylated-nitrogen. Zeta-potentials became more negative upon alkylation as a result of shielding of cationiccharges by hydrophobic alkyl-chains. Contact-killing of Gram-positive Staphylococci only occurred when the cationic-charge density exceeded 10{sup 16} cm{sup −2} and was carried by alkylated-nitrogen (electron-binding energy 401.3 eV). Gram-negative Escherichia coli was not killed upon contact with the coatings. There with this study reveals that cationic-charge density is neither appropriate nor sufficient to determine the ability of QUAT-coatings to kill adhering bacteria. Alternatively, the at.% of alkylated-nitrogen at 401.3 eV is proposed, as it reflects both

  13. Current approaches to improve the anticancer chemotherapy with alkylating agents: state of the problem in world and Ukraine.

    Directory of Open Access Journals (Sweden)

    Iatsyshyna A. P.

    2012-01-01

    Full Text Available Alkylating agents are frequently used in many established anticancer chemotherapies. They alkylate the genomic DNA at various sites. Alkylation of the guanine at the O6-position is cytotoxic, it has the strongest mutagenic potential, as well as can cause the tumor development. Alkyl groups at the O6-position of guanine are removed by the DNA repair enzyme O6-methylguanine-DNA methyltransferase (MGMT. The effectiveness of alkylating chemotherapy is limited by MGMT in cancer cells and adverse toxic side effects in normal cells. Different approaches consisting in the modulation of the MGMT expression and activity are under development now to improve the cancer chemotherapy. They include two main directions, in particular, the increase in chemosensitivity of cancer cells to alkylating drugs and the protection of normal cells from the toxic side effects of chemotherapy. This review is focused on current attempts to improve the alkylating chemotherapy of malignant tumours worldwide and state of the issue in Ukraine

  14. Lanthanide alkyl and silyl compounds: Synthesis, reactivity and catalysts for green

    Energy Technology Data Exchange (ETDEWEB)

    Pindwal, Aradhana [Iowa State Univ., Ames, IA (United States)

    2016-01-01

    The last few decades have witnessed enormous research in the field of organometallic lanthanide chemistry. Our research group has developed a few rare earth alkyl compounds containing tris(dimethylsilyl)methyl ligand and explored their reactivity. This thesis focusses on extending the study of lanthanide alkyl and silyl compounds to develop strategies for their synthesis and explore their reactivity and role as catalysts in processes such as hydrosilylation and cross-dehydrocoupling.

  15. Effects of alkylating agents on dopamine D(3) receptors in rat brain: selective protection by dopamine.

    Science.gov (United States)

    Zhang, K; Weiss, N T; Tarazi, F I; Kula, N S; Baldessarini, R J

    1999-11-13

    Dopamine D(3) receptors are structurally highly homologous to other D(2)-like dopamine receptors, but differ from them pharmacologically. D(3) receptors are notably resistant to alkylation by 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ), which readily alkylates D(2) receptors. We compared EEDQ with N-(p-isothiocyanatophenethyl)spiperone (NIPS), a selective D(2)-like receptor alkylating agent, for effects on D(3) and D(2) receptors in rat brain using autoradiographic analysis. Neither agent occluded D(3) receptors in vivo at doses that produced substantial blockade of D(2) receptors, even after catecholamine-depleting pretreatments. In vitro, however, D(3) receptors were readily alkylated by both NIPS (IC(50)=40 nM) and EEDQ (IC(50)=12 microM). These effects on D(3) sites were blocked by nM concentrations of dopamine, whereas microM concentrations were required to protect D(2) receptors from the alkylating agents. The findings are consistent with the view that alkylation of D(3) receptors in vivo is prevented by its high affinity for even minor concentrations of endogenous dopamine.

  16. Vaporization enthalpies of imidazolium based ionic liquids. A thermogravimetric study of the alkyl chain length dependence

    International Nuclear Information System (INIS)

    Verevkin, Sergey P.; Zaitsau, Dzmitry H.; Emel’yanenko, Vladimir N.; Ralys, Ricardas V.; Yermalayeu, Andrei V.; Schick, Christoph

    2012-01-01

    Highlights: ► Enthalpies of vaporization of ionic liquids were measured with thermogravimetry. ► We studied 1-alkyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide. ► The linear alkyl chain length was 4, 6, 8, 10, 12, 14, 16, and 18 C-atoms. ► A linear dependence on the chain length of the alkyl-imidazolium cation was found. - Abstract: Vaporization enthalpies for a series of ten ionic liquids (ILs) 1-alkyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide [C n mim][NTf 2 ], with the alkyl chain length n = 4, 6, 8, 10, 12, 14, 16, and 18 were determined using the thermogravimetric method. An internally consistent set of experimental data and vaporization enthalpies at 540 K was obtained. Vaporization enthalpies at 540 K have shown a linear dependence on the chain length of the alkyl-imidazolium cation in agreement with the experimental results measured previously with a quartz crystal microbalance. Ambiguity of Δ l g C pm o -values required for the extrapolation of experimental vaporization enthalpies to the reference temperature 298 K has been discussed.

  17. Conversion of 1-alkyl-2-acetyl-sn-glycerols to platelet activating factor and related phospholipids by rabbit platelets

    International Nuclear Information System (INIS)

    Blank, M.L.; Lee, T.; Cress, E.A.; Malone, B.; Fitzgerald, V.; Snyder, F.

    1984-01-01

    The metabolic pathway for 1-alkyl-2-acetyl-sn-glycerols, a recently discovered biologically active neutral lipid class, was elucidated in experiments conducted with rabbit platelets. The total lipid extract obtained from platelets incubated with 1-[1-,2- 3 H]alkyl-2-acetyl-sn-glycerols or 1-alkyl-2-[ 3 H]acetyl-sn-glycerols contained at least six metabolic products. The six metabolites, identified on the basis of chemical and enzymatic reactions combined with thin-layer or high-performance liquid chromatographic analyses, corresponded to 1-alkyl-sn-glycerols, 1-alkyl-2-acetyl-sn-glycero-3-phosphates, 1-alkyl-2-acyl(long-chain)-sn-glycero-3-phosphoethanolamines, 1-alkyl-2-acetyl-sn-glycero-3-phosphoethanolamines, 1-alkyl-2-acyl(long-chain)-sn-glycero-3-phosphocholines, and 1-alkyl-2-actyl-sn-glycero-3-phosphocholines (platelet activating factor). These results indicate that the metabolic pathway for alkylacetylglycerols involves reaction steps catalyzed by the following enzymatic activities: choline- and ethanolamine- phosphotransferases, acetyl-hydrolase, an acyltransferase, and a phosphotransferase. The step responsible for the biosynthesis of platelet activating factor would appear to be the most important reaction in this pathway and this product could explain the hypotensive activities previously described for alkylacetyl-(or propionyl)-glycerols. Of particular interest was the preference exhibited for the utilization of the 1-hexadecyl-2-acetyl-sn-glycerol species in the formation of platelet activating factor

  18. Read-across of ready biodegradability based on the substrate specificity of N-alkyl polypropylene polyamine-degrading microorganisms

    NARCIS (Netherlands)

    Geerts, R.; Ginkel, van C.G.; Plugge, C.M.

    2017-01-01

    The biodegradation of N-alkyl polypropylene polyamines (NAPPs) was studied using pure and mixed cultures to enable read-across of ready biodegradability test results. Two Pseudomonas spp. were isolated from activated sludge with N-oleyl alkyl propylene diamine and N-coco alkyl dipropylene triamine,

  19. SCC modification by use of amorphous nano-silica

    NARCIS (Netherlands)

    Quercia Bianchi, G.; Spiesz, P.R.; Hüsken, G.; Brouwers, H.J.H.

    2014-01-01

    In this study two different types of nano-silica (nS) were applied in self-compacting concrete (SCC), both having similar particle size distributions (PSD), but produced through two different processes: fumed powder silica and precipitated silica in colloidal suspension. The influence of nano-silica

  20. Agmatine attenuates silica-induced pulmonary fibrosis.

    Science.gov (United States)

    El-Agamy, D S; Sharawy, M H; Ammar, E M

    2014-06-01

    There is a large body of evidence that nitric oxide (NO) formation is implicated in mediating silica-induced pulmonary fibrosis. As a reactive free radical, NO may not only contribute to lung parenchymal tissue injury but also has the ability to combine with superoxide and form a highly reactive toxic species peroxynitrite that can induce extensive cellular toxicity in the lung tissues. This study aimed to explore the effect of agmatine, a known NO synthase inhibitor, on silica-induced pulmonary fibrosis in rats. Male Sprague Dawley rats were treated with agmatine for 60 days following a single intranasal instillation of silica suspension (50 mg in 0.1 ml saline/rat). The results revealed that agmatine attenuated silica-induced lung inflammation as it decreased the lung wet/dry weight ratio, protein concentration, and the accumulation of the inflammatory cells in the bronchoalveolar lavage fluid. Agmatine showed antifibrotic activity as it decreased total hydroxyproline content of the lung and reduced silica-mediated lung inflammation and fibrosis in lung histopathological specimen. In addition, agmatine significantly increased superoxide dismutase (p Agmatine also reduced silica-induced overproduction of pulmonary nitrite/nitrate as well as tumor necrosis factor α. Collectively, these results demonstrate the protective effects of agmatine against the silica-induced lung fibrosis that may be attributed to its ability to counteract the NO production, lipid peroxidation, and regulate cytokine effects. © The Author(s) 2014.

  1. Catalytic Asymmetric Alkylation of Aryl Heteroaryl Ketones

    NARCIS (Netherlands)

    Ortiz, Pablo; Harutyunyan, Syuzanna; del Hoyo, Ana

    Tertiary diarylmethanols are highly bioactive structural motifs. A new strategy to access chiral tertiary diarylmethanols through copper-catalyzed direct alkylation of (di)(hetero)aryl ketones by using Grignard reagents was developed. The low reactivity and the similarity of the enantiotopic faces

  2. Chlorodiethylaluminum supported on silica: A dinuclear aluminum surface species with bridging μ2-Cl-ligand as a highly efficient co-catalyst for the Ni-catalyzed dimerization of ethene

    KAUST Repository

    Kermagoret, Anthony

    2014-05-01

    Silica-supported chloro alkyl aluminum co-catalysts (DEAC@support) were prepared via Surface Organometallic Chemistry by contacting diethylaluminum chloride (DEAC) and high specific surface silica materials, i.e. SBA-15, MCM-41, and Aerosil SiO2. Such systems efficiently activate NiCl 2(PBu3)2 for catalytic ethene dimerization, with turnover frequency (TOF) reaching up to 498,000 molC2H4/ (molNi h) for DEAC@MCM-41. A detailed analysis of the DEAC@SBA-15 co-catalyst structure by solid-state aluminum-27 NMR at high-field (17.6 T and 20.0 T) and ultrafast spinning rates allows to detect six sites, characterized by a distribution of quadrupolar interaction principal values CQ and isotropic chemical shifts δiso. Identification of the corresponding Al-grafted structures was possible by comparison of the experimental NMR signatures with these calculated by DFT on a wide range of models for the aluminum species (mono- versus di-nuclear, mono- versus bis-grafted with bridging Cl or ethyl). Most of the sites were identified as dinuclear species with retention of the structure of DEAC, namely with the presence of μ2-Cl-ligands between two aluminum, and this probably explains the high catalytic performance of this silica-supported co-catalysts. © 2014 Elsevier Inc. All rights reserved.

  3. Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment

    Science.gov (United States)

    Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, James P.; Glavin, Daniel P.; Lazcano, Antonio; Bada, Jeffrey L.

    2011-01-01

    Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

  4. Nearest neighbor affects G:C to A:T transitions induced by alkylating agents.

    Science.gov (United States)

    Glickman, B W; Horsfall, M J; Gordon, A J; Burns, P A

    1987-01-01

    The influence of local DNA sequence on the distribution of G:C to A:T transitions induced in the lacI gene of E. coli by a series of alkylating agents has been analyzed. In the case of nitrosoguanidine, two nitrosoureas and a nitrosamine, a strong preference for mutation at sites proceeded 5' by a purine base was noted. This preference was observed with both methyl and ethyl donors where the predicted common ultimate alkylating species is the alkyl diazonium ion. In contrast, this preference was not seen following treatment with ethylmethanesulfonate. The observed preference for 5'PuG-3' site over 5'-PyG-3' sites corresponds well with alterations observed in the Ha-ras oncogene recovered after treatment with NMU. This indicates that the mutations recovered in the oncogenes are likely the direct consequence of the alkylation treatment and that the local sequence effects seen in E. coli also appear to occur in mammalian cells. PMID:3329097

  5. Nearest neighbor affects G:C to A:T transitions induced by alkylating agents

    Energy Technology Data Exchange (ETDEWEB)

    Glickman, B.W.; Horsfall, M.J.; Gordon, A.J.E.; Burns, P.A.

    1987-12-01

    The influence of local DNA sequence on the distribution of G:C to A:T transitions induced in the lacI gene of E. coli by a series of alkylating agents has been analyzed. In the case of nitrosoguanidine, two nitrosoureas and a nitrosamine, a strong preference for mutation at sites proceeded 5' by a purine base was noted. This preferences was observed with both methyl and ethyl donors where the predicted common ultimate alkylating species in the alkyl diazonium ion. In contrast, this preferences was not seen following treatment with ethylmethanesulfonate. The observed preference for 5'PuG-3' site over 5'-PyG-3' sites corresponds well with alterations observed in the Ha-ras oncogene recovered after treatment with NMU. This indicates that the mutations recovered in the oncogenes are likely the direct consequence of the alkylation treatment and that the local sequence effects seen in E. coli also appear to occur in mammalian cells.

  6. User-friendly aerobic reductive alkylation of iridium(III) porphyrin chloride with potassium hydroxide: scope and mechanism.

    Science.gov (United States)

    Zuo, Huiping; Liu, Zhipeng; Yang, Wu; Zhou, Zhikuan; Chan, Kin Shing

    2015-12-21

    Alkylation of iridium 5,10,15,20-tetrakistolylporphyrinato carbonyl chloride, Ir(ttp)Cl(CO) (1), with 1°, 2° alkyl halides was achieved to give (ttp)Ir-alkyls in good yields under air and water compatible conditions by utilizing KOH as the cheap reducing agent. The reaction rate followed the order: RCl < RBr < RI (R = alkyl), and suggests an SN2 pathway by [Ir(I)(ttp)](-). Ir(ttp)-adamantyl was obtained under N2 when 1-bromoadamantane was utilized, which could only undergo bromine atom transfer pathway. Mechanistic investigations reveal a substrate dependent pathway of SN2 or halogen atom transfer.

  7. All-silica nanofluidic devices for DNA-analysis fabricated by imprint of sol-gel silica with silicon stamp

    DEFF Research Database (Denmark)

    Mikkelsen, Morten Bo Lindholm; Letailleur, Alban A; Søndergård, Elin

    2011-01-01

    We present a simple and cheap method for fabrication of silica nanofluidic devices for single-molecule studies. By imprinting sol-gel materials with a multi-level stamp comprising micro- and nanofeatures, channels of different depth are produced in a single process step. Calcination of the imprin......We present a simple and cheap method for fabrication of silica nanofluidic devices for single-molecule studies. By imprinting sol-gel materials with a multi-level stamp comprising micro- and nanofeatures, channels of different depth are produced in a single process step. Calcination...... of the imprinted hybrid sol-gel material produces purely inorganic silica, which has very low autofluorescence and can be fusion bonded to a glass lid. Compared to top-down processing of fused silica or silicon substrates, imprint of sol-gel silica enables fabrication of high-quality nanofluidic devices without...

  8. Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles

    KAUST Repository

    Croissant, Jonas G.

    2017-01-13

    The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous silica nanoparticles (MSNs) have been an ongoing discussion in research circles. The reason for such a concern is that approved pharmaceutical products must not accumulate in the human body, to prevent severe and unpredictable side-effects. Here, the biorelated degradability and clearance of silicon and silica nanoparticles (NPs) are comprehensively summarized. The influence of the size, morphology, surface area, pore size, and surface functional groups, to name a few, on the degradability of silicon and silica NPs is described. The noncovalent organic doping of silica and the covalent incorporation of either hydrolytically stable or redox- and enzymatically cleavable silsesquioxanes is then described for organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica (PMO) NPs. Inorganically doped silica particles such as calcium-, iron-, manganese-, and zirconium-doped NPs, also have radically different hydrolytic stabilities. To conclude, the degradability and clearance timelines of various siliceous nanomaterials are compared and it is highlighted that researchers can select a specific nanomaterial in this large family according to the targeted applications and the required clearance kinetics.

  9. Functionalization of silica nanoparticles for polypropylene nanocomposites applications

    International Nuclear Information System (INIS)

    Bracho, Diego; Palza, Humberto; Quijada, Raul; Dougnac, Vivianne

    2011-01-01

    Synthetic silica nanospheres of different diameters produced via the sol-gel method were used in order to enhance the barrier properties of the polypropylene-silica nanocomposites. Modification of the silica surface by reaction with organic chlorosilanes was performed in order to improve the particles interaction with the polypropylene matrix and its dispersion. Unmodified and modified silica nanoparticles were characterized using electronic microscopy (TEM), elemental analysis, thermo gravimetric analysis (TGA), and solid state nuclear magnetic resonance (NMR) spectroscopy. Preliminary permeability tests of the polymer-silica nanocomposite films showed no significant change at low particles load (3 wt%) regardless its size or surface functionality, mainly because of the low aspect ratio of the silica nanospheres. However, it is expected that at a higher concentration of silica particles differences will be observed. (author)

  10. Toughening Mechanisms in Silica-Filled Epoxy Nanocomposites

    Science.gov (United States)

    Patel, Binay S.

    Epoxies are widely used as underfill resins throughout the microelectronics industry to mechanically couple and protect various components of flip-chip assemblies. Generally rigid materials largely surround underfill resins. Improving the mechanical and thermal properties of epoxy resins to better match those of their rigid counterparts can help extend the service lifetime of flip-chip assemblies. Recently, researchers have demonstrated that silica nanoparticles are effective toughening agents for lightly-crosslinked epoxies. Improvements in the fracture toughness of silica-filled epoxy nanocomposites have primarily been attributed to two toughening mechanisms: particle debonding with subsequent void growth and matrix shear banding. Various attempts have been made to model the contribution of these toughening mechanisms to the overall fracture energy observed in silica-filled epoxy nanocomposites. However, disparities still exist between experimental and modeled fracture energy results. In this dissertation, the thermal, rheological and mechanical behavior of eight different types of silica-filled epoxy nanocomposites was investigated. Each nanocomposite consisted of up to 10 vol% of silica nanoparticles with particle sizes ranging from 20 nm to 200 nm, with a variety of surface treatments and particle structures. Fractographical analysis was conducted with new experimental approaches in order to accurately identify morphological evidence for each proposed toughening mechanism. Overall, three major insights into the fracture behavior of real world silica-filled epoxy nanocomposites were established. First, microcracking was observed as an essential toughening mechanism in silica-filled epoxy nanocomposites. Microcracking was observed on the surface and subsurface of fractured samples in each type of silica-filled epoxy nanocomposite. The additional toughening contribution of microcracking to overall fracture energy yielded excellent agreement between experimental

  11. Synthesis of alkylated deoxyno irimycin and 1,5-dideoxy-1,5-iminoxylitol analogues:

    DEFF Research Database (Denmark)

    Szczepina, M.G.; Johnston, B.D; Yuan, Y.

    2004-01-01

    The syntheses of N-alkylated deoxynojirimycin and 1,5-dideoxy-1,5-iminoxylitol derivatives having either a D- or an L-erythritol-3-sulfate functionalized N-substituent are reported. The alkylating agent used was a cyclic sulfate derivative, whereby selective attack of the nitrogen atom at the least...

  12. Synthesis of alkyl phenols by means of radiofrequency plasmas

    International Nuclear Information System (INIS)

    Ropero, M.; Armas, F.; Iacocca, D.; Patino, P.

    1992-01-01

    New and promising possibilities in chemical synthesis have been opened through the interactions of oxygen plasmas with liquid alkyl benzene compounds. The alkyl phenols are the main products of the reaction mixtures (> 80%) oxygen, excited by radio-frequency (R.F.) is allowed to reach the surface of the liquid organic compound. The R.F. power supply is a Branson/IPC-PM 118. The substrate we have chosen are: methyl, ethyl, propyl, n-butyl, t-butyl, dimethyl and trimethyl benzenes. Under the same O 2 pressure and a power of 60 W, m-xylene and mesethylene behaved similarly. For all these substrates, values for the temperature of the liquid surface seem to indicate that oxidation tends to an optimum when P O 2 /vapor pressure (substrate) is higher than 20. In our experiments oxygen pressure in the reactor was about 0.2 Torr. Oxidation is basically attributed to O 3 P and the addition to alkyl benzenes selectively takes place on the aromatic rings, at low reactor pressure. The oxygen atom impinges on the liquid surface and epoxy intermediates could be formed. These intermediates then progress to the corresponding phenols. (author)

  13. Mechanism of Phenol Alkylation in Zeolite H-BEA Using In Situ Solid-State NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Zhenchao [Institute; Shi, Hui [Institute; Wan, Chuan [Institute; Hu, Mary Y. [Institute; Liu, Yuanshuai [Department; Mei, Donghai [Institute; Camaioni, Donald M. [Institute; Hu, Jian Zhi [Institute; Lercher, Johannes A. [Institute; Department

    2017-06-27

    Alkylation of phenolic compounds in the liquid phase is of fundamental and practical importance to the conversion of biomass-derived feedstocks into fuels and chemicals. In this work, the reaction mechanism for phenol alkylation with cyclohexanol and cyclohexene has been investigated on a commercial HBEA zeolite by in situ 13C MAS NMR, using decalin as the solvent. From the variable temperature 13C MAS NMR measurements of phenol and cyclohexanol adsorption on HBEA from decalin solutions, it is shown that the two molecules have similar adsorption strength in the HBEA pore. Phenol alkylation with cyclohexanol, however, becomes significantly measurable only after cyclohexanol is largely converted to cyclohexene via dehydration. This is in contrast to the initially rapid alkylation of phenol when using cyclohexene as the co-reactant. 13C isotope scrambling results demonstrate that the electrophile, presumably cyclohexyl carbenium ion, is directly formed in a protonation step when cyclohexene is the co-reactant, but requires re-adsorption of the alcohol dehydration product, cyclohexene, when cyclohexanol dimer is the dominant surface species (e.g., at 0.5 M cyclohexanol concentration) that is unable to generate carbenium ion. At the initial reaction stage of phenol-cyclohexanol alkylation on HBEA, the presence of the cyclohexanol dimer species hinders the adsorption of cyclohexene at the Brønsted acid site and the subsequent activation of the more potent electrophile (carbenium ion). Isotope scrambling data also show that intramolecular rearrangement of cyclohexyl phenyl ether, the O-alkylation product, does not significantly contribute to the formation of C-alkylation products.

  14. Polar silica-based stationary phases. Part II- Neutral silica stationary phases with surface bound maltose and sorbitol for hydrophilic interaction liquid chromatography.

    Science.gov (United States)

    Rathnasekara, Renuka; El Rassi, Ziad

    2017-07-28

    Two neutral polyhydroxylated silica bonded stationary phases, namely maltose-silica (MALT-silica) and sorbitol-silica (SOR-silica), have been introduced and chromatographically characterized in hydrophilic interaction liquid chromatography (HILIC) for a wide range of polar compounds. The bonding of the maltose and sorbitol to the silica surface was brought about by first converting bare silica to an epoxy-activated silica surface via reaction with γ-glycidoxypropyltrimethoxysilane (GPTMS) followed by attaching maltose and sorbitol to the epoxy surface in the presence of the Lewis acid catalyst BF 3 .ethereate. Both silica based columns offered the expected retention characteristics usually encountered for neutral polar surface. The retention mechanism is majorly based on solute' differential partitioning between an organic rich hydro-organic mobile phase (e.g., ACN rich mobile phase) and an adsorbed water layer on the surface of the stationary phase although additional hydrogen bonding was also responsible in some cases for solute retention. The MALT-silica column proved to be more hydrophilic and offered higher retention, separation efficiency and resolution than the SOR-silica column among the tested polar solutes such as derivatized mono- and oligosaccharides, weak phenolic acids, cyclic nucleotide monophosphate and nucleotide-5'-monophosphates, and weak bases, e.g., nucleobases and nucleosides. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Melamine-bridged alkyl resorcinol modified urea - formaldehyde resin for bonding hardwood plywood

    Science.gov (United States)

    Chung-Yun Hse; Mitsuo Higuchi

    2010-01-01

    A powdery product was obtained by the reaction of methylolated melamine with alkyl resorcinols to form melamine-bridged alkyl resorcinols (MARs). The effects of the addition of this powder on the bonding strength and formaldehyde emission of urea–formaldehyde (UF) resins were investigated. Three types of UF resins with a formaldehyde/urea molar ratio of 1.3 synthesized...

  16. Modulation of the toxicity and antitumour activity of alkylating drugs by steroids.

    OpenAIRE

    Shepherd, R.; Harrap, K. R.

    1982-01-01

    The steroids prednisolone and progesterone significantly altered the therapeutic indices of the alkylating agents, nitrogen mustard, melphalan, cyclophosphamide, phenyl acetic mustard and chlorambucil. For nitrogen mustard, chlorambucil and phenyl acetic mustard, prednisolone reduced host toxicity in the rat and enhanced the antitumour effectiveness against alkylating-agent-resistant strains of the Yoshida sarcoma and Walker carcinosarcoma. Progesterone also increased the therapeutic index of...

  17. Glutamine deficiency induces DNA alkylation damage and sensitizes cancer cells to alkylating agents through inhibition of ALKBH enzymes.

    Directory of Open Access Journals (Sweden)

    Thai Q Tran

    2017-11-01

    Full Text Available Driven by oncogenic signaling, glutamine addiction exhibited by cancer cells often leads to severe glutamine depletion in solid tumors. Despite this nutritional environment that tumor cells often experience, the effect of glutamine deficiency on cellular responses to DNA damage and chemotherapeutic treatment remains unclear. Here, we show that glutamine deficiency, through the reduction of alpha-ketoglutarate, inhibits the AlkB homolog (ALKBH enzymes activity and induces DNA alkylation damage. As a result, glutamine deprivation or glutaminase inhibitor treatment triggers DNA damage accumulation independent of cell death. In addition, low glutamine-induced DNA damage is abolished in ALKBH deficient cells. Importantly, we show that glutaminase inhibitors, 6-Diazo-5-oxo-L-norleucine (DON or CB-839, hypersensitize cancer cells to alkylating agents both in vitro and in vivo. Together, the crosstalk between glutamine metabolism and the DNA repair pathway identified in this study highlights a potential role of metabolic stress in genomic instability and therapeutic response in cancer.

  18. Glutamine deficiency induces DNA alkylation damage and sensitizes cancer cells to alkylating agents through inhibition of ALKBH enzymes.

    Science.gov (United States)

    Tran, Thai Q; Ishak Gabra, Mari B; Lowman, Xazmin H; Yang, Ying; Reid, Michael A; Pan, Min; O'Connor, Timothy R; Kong, Mei

    2017-11-01

    Driven by oncogenic signaling, glutamine addiction exhibited by cancer cells often leads to severe glutamine depletion in solid tumors. Despite this nutritional environment that tumor cells often experience, the effect of glutamine deficiency on cellular responses to DNA damage and chemotherapeutic treatment remains unclear. Here, we show that glutamine deficiency, through the reduction of alpha-ketoglutarate, inhibits the AlkB homolog (ALKBH) enzymes activity and induces DNA alkylation damage. As a result, glutamine deprivation or glutaminase inhibitor treatment triggers DNA damage accumulation independent of cell death. In addition, low glutamine-induced DNA damage is abolished in ALKBH deficient cells. Importantly, we show that glutaminase inhibitors, 6-Diazo-5-oxo-L-norleucine (DON) or CB-839, hypersensitize cancer cells to alkylating agents both in vitro and in vivo. Together, the crosstalk between glutamine metabolism and the DNA repair pathway identified in this study highlights a potential role of metabolic stress in genomic instability and therapeutic response in cancer.

  19. Magnetic core-shell silica particles

    NARCIS (Netherlands)

    Claesson, E.M.

    2007-01-01

    This thesis deals with magnetic silica core-shell colloids and related functionalized silica structures. Synthesis routes have been developed and optimized. The physical properties of these colloids have been investigated, such as the magnetic dipole moment, dipolar structure formation and

  20. Regeneration of zeolite catalysts of isobutane alkylation with butenes

    Energy Technology Data Exchange (ETDEWEB)

    Manza, I.A.; Tsupryk, I.N.; Bartyshevskii, V.A.; Gaponenko, O.I.; Petrilyak, K.I.

    1986-12-10

    The industrial adoption of alkylation of isoalkanes with alkenes is held back by the rapid and irreversible deactivation of the zeolite catalysts appropriate to the process. This paper is aimed specifically at the restoration of the catalytic activity and increase in the service life of zeolite alkylation catalysts. The catalyst chosen for the investigation was HLaCaNaX zeolite both unmodified and modified with various multivalence cations. The thermochemical and oxidative regeneration process as well as the equipment utilized are described. Both the advantages and the drawbacks of the method are given; explanations for the possibly irreversible losses of the catalytic properties in the regenerated zeolites are also put forward.

  1. Direct α-alkylation of ketones with alcohols in water.

    Science.gov (United States)

    Xu, Guoqiang; Li, Qiong; Feng, Jiange; Liu, Qiang; Zhang, Zuojun; Wang, Xicheng; Zhang, Xiaoyun; Mu, Xindong

    2014-01-01

    The direct α-alkylation of ketones with alcohols has emerged as a new green protocol to construct C-C bonds with H2 O as the sole byproduct. In this work, a very simple and convenient Pd/C catalytic system for the direct α-alkylation of ketones with primary alcohols in pure water is developed. Based on this catalytic system, aqueous mixtures of dilute acetone, 1-butanol, and ethanol (mimicking ABE fermentation products) can be directly transformed into C5 -C11 or longer-chain ketones and alcohols, which are precursors to fuels. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Ionic liquid and solid HF equivalent amine-poly(hydrogen fluoride) complexes effecting efficient environmentally friendly isobutane-isobutylene alkylation.

    Science.gov (United States)

    Olah, George A; Mathew, Thomas; Goeppert, Alain; Török, Béla; Bucsi, Imre; Li, Xing-Ya; Wang, Qi; Marinez, Eric R; Batamack, Patrice; Aniszfeld, Robert; Prakash, G K Surya

    2005-04-27

    Isoparaffin-olefin alkylation was investigated using liquid as well as solid onium poly(hydrogen fluoride) catalysts. These new immobilized anhydrous HF catalysts contain varied amines and nitrogen-containing polymers as complexing agents. The liquid poly(hydrogen fluoride) complexes of amines are typical ionic liquids, which are convenient media and serve as HF equivalent catalysts with decreased volatility for isoparaffin-olefin alkylation. Polymeric solid amine:poly(hydrogen fluoride) complexes are excellent solid HF equivalents for similar alkylation acid catalysis. Isobutane-isobutylene or 2-butene alkylation gave excellent yields of high octane alkylates (up to RON = 94). Apart from their excellent catalytic performance, the new catalyst systems significantly reduce environmental hazards due to the low volatility of complexed HF. They represent a new, "green" class of catalyst systems for alkylation reactions, maintaining activity of HF while minimizing its environmental hazards.

  3. Efficient synthesis of N-alkyl-2,7-dihalocarbazoles by simultaneous carbazole ring closure and N-alkylation

    Czech Academy of Sciences Publication Activity Database

    Výprachtický, Drahomír; Kmínek, Ivan; Pokorná, Veronika; Cimrová, Věra

    2012-01-01

    Roč. 68, č. 25 (2012), s. 5075-5080 ISSN 0040-4020 R&D Projects: GA MŠk(CZ) 1M06031; GA ČR GAP106/12/0827 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : carbazole ring closure * carbazole alkylation * heterocycles Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 2.803, year: 2012

  4. Tripodal (N-alkylated) CMP(O) and malonamide ligands: synthesis, extraction of metal ions, and potentiometric studies

    International Nuclear Information System (INIS)

    Janczewski, D.; Reinhoudt, D.N.; Verboom, W.; Malinowska, E.; Pietrzak, M.; Hill, C.; Allignol, C.

    2007-01-01

    Tripodal ligands build on the C-pivot (9b-e, 13b-d, and 17a-d) and tri-alkyl-benzene platforms (10a,b, 11, 12, 14a,b, and 18a,b) bearing (N-alkylated) carbamoyl-methyl-phosphine oxide (CMPO), carbamoyl-methyl-phosphonate (CMP), and malonamide moieties were synthesized. Extraction studies with Am 3+ and Eu 3+ show that in general there is a positive influence of the N-alkyl substituents in C-pivot CMP(O) ligands on the D(distribution) coefficients. The tri-alkyl-benzene CMPO ligands 10a,b, 11, and 12 have considerably larger D coefficients than the corresponding C-pivot analogues 9a-e, although hardly having any selectivity, while N-alkylation gives rise to smaller D coefficients. Although less effective the extraction behavior of the C-pivot CMP analogues 13b-d shows more or less the same trend as the corresponding CMPO ligands 9b-e upon substitution of the carboxamide N-atom with different alkyl chains. The different malonamide ligands 17a-d and 18a,b are bad extractants, while N-alkylation makes them even worse. Potentiometric studies of CMP(O) and malonamide ligands in polymeric membranes on Pb 2+ , Cu 2+ , Ca 2+ , Mg 2+ , Na + , and K + salts revealed that N-alkyl substituents increase the stability constants of ion-ionophore complexes compared to unsubstituted ligands. In polymeric membrane electrodes the ligands induce a selectivity pattern that differs significantly from the so-called Hofmeister series, giving the highest selectivity coefficients for UO 2 2+ among all examined cations (Pb 2+ , Cu 2+ , Ca 2+ , Mg 2+ , Na + , K + ). (authors)

  5. Systematic Evaluation of Protein Reduction and Alkylation Reveals Massive Unspecific Side Effects by Iodine-containing Reagents.

    Science.gov (United States)

    Müller, Torsten; Winter, Dominic

    2017-07-01

    Reduction and alkylation of cysteine residues is part of virtually any proteomics workflow. Despite its frequent use, up to date no systematic investigation of the impact of different conditions on the outcome of proteomics studies has been performed. In this study, we compared common reduction reagents (dithiothreitol, tris-(2-carboxyethyl)-phosphine, and β-mercaptoethanol) and alkylation reagents (iodoacetamide, iodoacetic acid, acrylamide, and chloroacetamide). Using in-gel digests as well as SAX fractionated in-solution digests of cytosolic fractions of HeLa cells, we evaluated 13 different reduction and alkylation conditions resulting in considerably varying identification rates. We observed strong differences in offsite alkylation reactions at 7 amino acids as well as at the peptide N terminus, identifying single and double adducts of all reagents. Using dimethyl labeling, mass tolerant searches, and synthetic peptide experiments, we identified alkylation of methionine residues by iodine-containing alkylation reagents as one of the major factors for the differences. We observed differences of more than 9-fold in numbers of identified methionine-containing peptide spectral matches for in-gel digested samples between iodine- and noniodine-containing alkylation reagents. This was because of formation of carbamidomethylated and carboxymethylated methionine side chains and a resulting prominent neutral loss during ESI ionization or in MS/MS fragmentation, strongly decreasing identification rates of methionine-containing peptides. We achieved best results with acrylamide as alkylation reagent, whereas the highest numbers of peptide spectral matches were obtained when reducing with dithiothreitol and β-mercaptoethanol for the in-solution and the in-gel digested samples, respectively. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  6. ALKBH7 drives a tissue and sex-specific necrotic cell death response following alkylation-induced damage

    Science.gov (United States)

    Jordan, Jennifer J; Chhim, Sophea; Margulies, Carrie M; Allocca, Mariacarmela; Bronson, Roderick T; Klungland, Arne; Samson, Leona D; Fu, Dragony

    2017-01-01

    Regulated necrosis has emerged as a major cell death mechanism in response to different forms of physiological and pharmacological stress. The AlkB homolog 7 (ALKBH7) protein is required for regulated cellular necrosis in response to chemotherapeutic alkylating agents but its role within a whole organism is unknown. Here, we show that ALKBH7 modulates alkylation-induced cellular death through a tissue and sex-specific mechanism. At the whole-animal level, we find that ALKBH7 deficiency confers increased resistance to MMS-induced toxicity in male but not female mice. Moreover, ALKBH7-deficient mice exhibit protection against alkylation-mediated cytotoxicity in retinal photoreceptor and cerebellar granule cells, two cell types that undergo necrotic death through the initiation of the base excision repair pathway and hyperactivation of the PARP1/ARTD1 enzyme. Notably, the protection against alkylation-induced cerebellar degeneration is specific to ALKBH7-deficient male but not female mice. Our results uncover an in vivo role for ALKBH7 in mediating a sexually dimorphic tissue response to alkylation damage that could influence individual responses to chemotherapies based upon alkylating agents. PMID:28726787

  7. Fractionated dose studies with X-rays and various alkylating agents in P388 mouse lymphoma cells

    International Nuclear Information System (INIS)

    Anderson, D.

    1981-01-01

    The fractionated dose technique has been used in P388F cells to examine the effects of X-rays and four alkylating agents on survival and induction of 5-iodo-2-deoxyuridine (IudR) resistant variants. Fractionation intervals up to 5 1/2 h were used for X-rays and for the alkylating agents up to 192 h. Fractionation of the X-ray dose resulted in a sparing effect for survival and variant induction. A sparing effect was also observed for survival after treatment with alkylating agents. However, variant frequencies were observed as large as or greater than those produced by the full doses of alkylating agents. For such agents this would suggest that survival and variant induction are independent events. Differences in the effects of X-rays and alkylating agents cannot be explained by differences in growth rate or the recovery of viability after treatment

  8. Fractionated dose studies with X-rays and various alkylating agents in P388 mouse lymphoma cells

    International Nuclear Information System (INIS)

    Anderson, D.

    1981-01-01

    The fractionated dose technique was used in P388F cells to examine the effects of X-rays and four alkylating agents on survival and induction of 5-iodo-2-deoxyuridine (IudR) resistant variants. Fractionation intervals up to 51/2 h were used for X-rays and for the alkylating agents up to 192 h. Fractionation of the X-ray dose resulted in a sparing effect for survival and variant induction. A sparing effect was also observed for survival after treatment with alkylating agents. However, variant frequencies were observed as large as or greater than those produced by the full doses of alkylating agents. For such agents this would suggest that survival and variant induction are independent events. Differences in the effects of X-rays and alkylating agents cannot be explained by differences in growth rate or the recovery of viability after treatment. (author)

  9. Protonation of 1-alkyl-2-allyllithium-0-carboranes and 1-methyl-2-allylmaonesium chloride-0-carborane

    International Nuclear Information System (INIS)

    Ivanova, N.N.; Kazantsev, A.V.; Zakharkin, L.I.

    1975-01-01

    The ratio of 1-alkyl-2-allyl and 1-alkyl-2-propenyl-0-carboranes generated in protonation of 1-alkyl-2-lithium allyl-0-carboranes with various protolytic agents in ether, THF and liquid ammonia depends on the nature of protolytic agent and solvent. The rat:o of these allyl and propenyl isomers is also affected by steric effects of the protolytic agent and 0-carborane nucleus

  10. High yield silicon carbide from alkylated or arylated pre-ceramic polymer

    International Nuclear Information System (INIS)

    Baney, R.H.; Gaul, J.H.

    1982-01-01

    Alkylated or arylated methylpolysilanes which exhibit ease of handling and are used to obtain silicon carbide ceramic materials in high yields contain 0 to 60 mole percent (CH 3 ) 2 Si double bond units and 40 to 100 mole percent CH 3 Si triple bond units, wherein there is also bonded to the silicon atoms other silicon atoms and additional alkyl radicals of 1 to 4 carbon atoms or phenyl. They may be prepared by reaction of a Grignard reagent RMgX, where X is halogen and R is Csub(1-4)-alkyl or phenyl, with a starting material which is a solid at 25 0 C, and is identical to the product except that the remaining bonds on the silicon atoms are attached to another silicon atom, or a chlorine or a bromine atom. Ceramics result from heating the polysilane products to 1200 0 C, optionally with fillers. (author)

  11. Anomalous enthalpy relaxation in vitreous silica

    DEFF Research Database (Denmark)

    Yue, Yuanzheng

    2015-01-01

    scans. It is known that the liquid fragility (i.e., the speed of the viscous slow-down of a supercooled liquid at its Tg during cooling) has impact on enthalpy relaxation in glass. Here, we find that vitreous silica (as a strong system) exhibits striking anomalies in both glass transition and enthalpy...... relaxation compared to fragile oxide systems. The anomalous enthalpy relaxation of vitreous silica is discovered by performing the hyperquenching-annealing-calorimetry experiments. We argue that the strong systems like vitreous silica and vitreous Germania relax in a structurally cooperative manner, whereas...... the fragile ones do in a structurally independent fashion. We discuss the origin of the anomalous enthalpy relaxation in the HQ vitreous silica....

  12. Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts.

    Science.gov (United States)

    Khokarale, Santosh Govind; He, Jian; Schill, Leonhard; Yang, Song; Riisager, Anders; Saravanamurugan, Shunmugavel

    2018-02-22

    Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO 2 in methanol at 220 °C and 50 bar H 2 . A synergistic effect of Ni increased the yield of MP significantly when using Fe-Ni/ZrO 2 instead of Fe/ZrO 2 alone. Moreover, the ZrO 2 support contributed to improve the yield as a phase transition of ZrO 2 from tetragonal to monoclinic occurred after metal doping giving rise to fine dispersion of the Fe and Ni on the ZrO 2 , resulting in a higher catalytic activity of the material. Interestingly, it was observed that Fe-Ni/ZrO 2 also effectively catalyzed methanol reforming to produce H 2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N 2 instead of H 2 . Fe-Ni/ZrO 2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl propionates in high yields around 70 %. No loss of activity of Fe-Ni/ZrO 2 occurred in five consecutive reaction runs demonstrating the high durability of the catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Mesoporous Silica from Rice Husk Ash

    Directory of Open Access Journals (Sweden)

    S.A. Mandavgane

    2010-12-01

    Full Text Available Mesoporous silica is used as a raw material in several areas: in preparation of catalysts, in inks, as aconcrete hardening accelerator, as a component of detergents and soaps, as a refractory constituent etc.Sodium silicate is produced by reacting rice hull ash (RHA with aqueous NaOH and silica is precipitatedfrom the sodium silicate by acidification. In the present work, conversion of about 90% of silica containedin RHA into sodium silicate was achieved in an open system at temperatures of about 100 °C. The resultsshowed that silica obtained from RHA is mesoporous, has a large surface area and small particle size.Rice Husk is usually mixed with coal and this mixture is used for firing boilers. The RHA therefore, usuallycontains carbon particles. Activated carbon embedded on silica has been prepared using the carbon alreadypresent in RHA. This carbon shows good adsorption capacity. ©2010 BCREC UNDIP. All rights reserved(Received: 25th April 2010, Revised: 17th June 2010, Accepted: 24th June 2010[How to Cite: V.R. Shelke, S.S. Bhagade, S.A. Mandavgane. (2010. Mesoporous Silica from Rice Husk Ash. Bulletin of Chemical Reaction Engineering and Catalysis, 5 (2: 63-67. doi:10.9767/bcrec.5.2.793.63-67

  14. Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

    Science.gov (United States)

    He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

    2016-06-08

    Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability.

  15. Practical Hydrogen Loading of Air Silica Fibres

    DEFF Research Database (Denmark)

    Sørensen, Henrik Rokkjær; Jensen, Jesper Bevensee; Jensen, Jesper Bo Damm

    2005-01-01

    A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown.......A method for hydrogen-loading air-silica optical fibres has been developed allowing out-diffusion times comparable to standard step-index fibres. Examples of the first grating written in Ge-doped air-silica fibres using a 266nm UV-laser are shown....

  16. Conformational Restriction of Peptides Using Dithiol Bis-Alkylation.

    Science.gov (United States)

    Peraro, L; Siegert, T R; Kritzer, J A

    2016-01-01

    Macrocyclic peptides are highly promising as inhibitors of protein-protein interactions. While many bond-forming reactions can be used to make cyclic peptides, most have limitations that make this chemical space challenging to access. Recently, a variety of cysteine alkylation reactions have been used in rational design and library approaches for cyclic peptide discovery and development. We and others have found that this chemistry is versatile and robust enough to produce a large variety of conformationally constrained cyclic peptides. In this chapter, we describe applications, methods, mechanistic insights, and troubleshooting for dithiol bis-alkylation reactions for the production of cyclic peptides. This method for efficient solution-phase macrocyclization is highly useful for the rapid production and screening of loop-based inhibitors of protein-protein interactions. © 2016 Elsevier Inc. All rights reserved.

  17. Alkylation of isobutane by ethylene: A thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Goupil, J.M.; Poirier, J.L.; Cornet, D. (Univ. of Caen (France). Lab. Catalyse et Spectrochimie)

    1994-03-01

    Alkylation of isobutane by ethylene produces mainly hexanes, but a variety of other compounds, alkanes or alkenes, may be formed by secondary reactions such as successive alkylations, isomerization, and ethylene polymerization. The equilibrium distribution of products is evaluated in the temperature range 280--680 K and at various initial compositions and pressures. Isomer groups are treated using Alberty's formulation. Calculations show that alkenes are thermodynamically unstable under usual reaction conditions. The equilibrium amounts of alkanes are such that C[sub 6] [much gt] C[sub 8] [much gt] C[sub 10] and heavy alkanes also appear unstable. The selective formation of particular isomers (dimethylbutanes, trimethylpentanes) is also integrated in the equilibrium equations. The calculated compositions (C[sub 6]:C[sub 8]:C[sub 10]) are compared with experimental data.

  18. Effect of support on hydro-metathesis of propene: A comparative study of W(CH 3 ) 6 anchored to silica vs. silica-alumina

    KAUST Repository

    Tretiakov, Mykyta; Samantaray, Manoja; Saidi, Aya; Basset, Jean-Marie

    2018-01-01

    Hydro-metathesis of propene was carried out by using well-defined W(CH3)6 supported on silica and silica-alumina. It was observed that W(CH3)6 supported silica-alumina catalyst is much better (TON 4577) than the silica supported catalyst (TON 2104

  19. Altering the concentration of silica tunes the functional properties of collagen-silica composite scaffolds to suit various clinical requirements.

    Science.gov (United States)

    Perumal, Sathiamurthi; Ramadass, Satiesh Kumar; Gopinath, Arun; Madhan, Balaraman; Shanmugam, Ganesh; Rajadas, Jayakumar; Mandal, Asit Baran

    2015-12-01

    The success of a tissue engineering scaffold depends on a fine balance being achieved between the physicochemical and biological properties. This study attempts to understand the influence of silica concentration on the functional properties of collagen-silica (CS) composite scaffolds for soft tissue engineering applications. Increasing the ratio of silica to collagen (0.25, 0.5, 0.75, 1.0, 1.25, 1.5 and 2.0 w/w) gave a marked advantage in terms of improving the water uptake and compressive modulus of the CS scaffolds, while also enhancing the biological stability and the turnover time. With increase in silica concentration the water uptake and compressive modulus increased concurrently, whereas it was not so for surface porous architecture and biocompatibility which are crucial for cell adhesion and infiltration. Silica:collagen ratio of ≤1 exhibits favourable surface biocompatibility, and any further increase in silica concentration has a detrimental effect. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Ada response - a strategy for repair of alkylated DNA in bacteria.

    Science.gov (United States)

    Mielecki, Damian; Grzesiuk, Elżbieta

    2014-06-01

    Alkylating agents are widespread in the environment and also occur endogenously. They can be cytotoxic or mutagenic to the cells introducing alkylated bases to DNA or RNA. All organisms have evolved multiple DNA repair mechanisms to counteract the effects of DNA alkylation: the most cytotoxic lesion, N(3)-methyladenine (3meA), is excised by AlkA glycosylase initiating base excision repair (BER); toxic N(1)-methyladenine (1meA) and N(3)-methylcytosine (3meC), induced in DNA and RNA, are removed by AlkB dioxygenase; and mutagenic and cytotoxic O(6)-methylguanine (O(6) meG) is repaired by Ada methyltransferase. In Escherichia coli, Ada response involves the expression of four genes, ada, alkA, alkB, and aidB, encoding respective proteins Ada, AlkA, AlkB, and AidB. The Ada response is conserved among many bacterial species; however, it can be organized differently, with diverse substrate specificity of the particular proteins. Here, an overview of the organization of the Ada regulon and function of individual proteins is presented. We put special effort into the characterization of AlkB dioxygenases, their substrate specificity, and function in the repair of alkylation lesions in DNA/RNA. © 2014 The Authors. FEMS Microbiology Letters published by John Wiley & Sons Ltd on behalf of Federation of European Microbiological Societies.

  1. Poly(vinyl chloride-grafted multi-walled carbon nanotubes via Friedel-Crafts alkylation

    Directory of Open Access Journals (Sweden)

    2010-11-01

    Full Text Available A novel approach was developed for the surface modification of the multi-walled carbon nanotubes (MWCNTs with high percentage of grafting (PG% by the grafting of polymer via the Friedel-Crafts alkylation. The graft reaction conditions, such as the amount of catalyst added, the reaction temperature, and the reaction time were optimized for the Friedel-Crafts alkylation of the MWCNTs with poly(vinyl chloride (PVC with anhydrous aluminum chloride (AlCl3 as catalyst in chloroform (CHCl3. The Fourier Transform Infrared (FT-IR, Raman, and thermogravimetric (TGA analysis showed that PVC had been successfully grafted onto MWCNTs both at the ends and on the sidewalls by the proposed Friedel-Crafts alkylation. The PVC grafted MWCNTs (PVC-MWCNTs could be dispersed well in organic solvent and the dispersion was more stable.

  2. Silica-Coated Liposomes for Insulin Delivery

    OpenAIRE

    Neelam Dwivedi; M. A. Arunagirinathan; Somesh Sharma; Jayesh Bellare

    2010-01-01

    Liposomes coated with silica were explored as protein delivery vehicles for their enhanced stability and improved encapsulation efficiency. Insulin was encapsulated within the fluidic phosphatidylcholine lipid vesicles by thin film hydration at pH 2.5, and layer of silica was formed above lipid bilayer by acid catalysis. The presence of silica coating and encapsulated insulin was identified using confocal and electron microscopy. The native state of insulin present in the formulation was evid...

  3. Mechanism of alkylation of isobutane by olefins in the presence of sulfuric acid

    Energy Technology Data Exchange (ETDEWEB)

    Baiburskii, V.L.; Khadzhiev, S.N.; Ovsyannikov, V.P.

    1992-05-10

    The authors attempted here to examine the mechanism of alkylation of isobutane by olefins in the presence of sulfuric acid in terms of an initial stage of activation of isoparaffin. The version of formation of tert-alkyl cations and the role of the catalyst in this stage were analyzed. 10 refs., 1 fig., 1 tab.

  4. A new route alpha-alkyl-alpha-fluoromethylenebisphosphonates

    Czech Academy of Sciences Publication Activity Database

    Beier, Petr; Opekar, Stanislav; Zibinsky, M.; Bychinskaya, I.; Prakash, G. K. S.

    2011-01-01

    Roč. 9, č. 11 (2011), s. 4035-4038 ISSN 1477-0520 R&D Projects: GA ČR GP203/08/P310 Institutional research plan: CEZ:AV0Z40550506 Keywords : fluorine * phosphonate * alkylation Subject RIV: CC - Organic Chemistry Impact factor: 3.696, year: 2011

  5. Alkylation of human hair keratin for tunable hydrogel erosion and drug delivery in tissue engineering applications.

    Science.gov (United States)

    Han, Sangheon; Ham, Trevor R; Haque, Salma; Sparks, Jessica L; Saul, Justin M

    2015-09-01

    Polymeric biomaterials that provide a matrix for cell attachment and proliferation while achieving delivery of therapeutic agents are an important component of tissue engineering and regenerative medicine strategies. Keratins are a class of proteins that have received attention for numerous tissue engineering applications because, like other natural polymers, they promote favorable cell interactions and have non-toxic degradation products. Keratins can be extracted from various sources including human hair, and they are characterized by a high percentage of cysteine residues. Thiol groups on reductively extracted keratin (kerateine) form disulfide bonds, providing a more stable cross-linked hydrogel network than oxidatively extracted keratin (keratose) that cannot form disulfide crosslinks. We hypothesized that an iodoacetamide alkylation (or "capping") of cysteine thiol groups on the kerateine form of keratin could be used as a simple method to modulate the levels of disulfide crosslinking in keratin hydrogels, providing tunable rates of gel erosion and therapeutic agent release. After alkylation, the alkylated kerateines still formed hydrogels and the alkylation led to changes in the mechanical and visco-elastic properties of the materials consistent with loss of disulfide crosslinking. The alkylated kerateines did not lead to toxicity in MC3T3-E1 pre-osteoblasts. These cells adhered to keratin at levels comparable to fibronectin and greater than collagen. Alkylated kerateine gels eroded more rapidly than non-alkylated kerateine and this control over erosion led to tunable rates of delivery of rhBMP-2, rhIGF-1, and ciprofloxacin. These results demonstrate that alkylation of kerateine cysteine residues provides a cell-compatible approach to tune rates of hydrogel erosion and therapeutic agent release within the context of a naturally-derived polymeric system. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  6. Mechanistic Insights into Solvent and Ligand Dependency in Cu(I)-Catalyzed Allylic Alkylation with gem-Diborylalkanes.

    Science.gov (United States)

    Zhang, Qi; Wang, Bing; Liu, Jia-Qin; Fu, Yao; Wu, Yu-Cheng

    2018-01-19

    The recent Cu-catalyzed allylic substitution reaction between gem-diboryalkane and allyl electrophiles shows intriguing solvent and ligand-controlled regioselectivity. The α-alkylation product was obtained in DMF solvent, while γ-alkylation product was obtained in dioxane solvent and the dioxane and NHC ligand situation. In the present study, density functional theory calculations have been used to investigate the reaction mechanism and origin of the regioselectivity. For both dioxane and DMF, γ-alkylation undergoes successive oxidative addition (CH 2 Bpin trans to leaving group) and direct Cγ-C reductive elimination. The α-alkylation is found to undergo oxidative addition (CH 2 Bpin trans to leaving group), isomerization, and Cα-C reductive elimination rather than the previously proposed oxidative addition (-CH 2 Bpin cis to the leaving group) and Cα-C reductive elimination. The γ-alkylation and α-alkylation is, respectively, favorable for dioxane and DMF solvent, which is consistent with the γ- and α-selectivity in experiment. The solvent interferes the isomerization step, thereby affects the relative facility of the α- and γ-alkylation. Further investigation shows that η 1 -intermediate formation promoted by solvent is the rate-determining step of the isomerization. The stronger electron-donating ability of DMF than dioxane facilitates the η 1 -intermediate formation and finally results in the easier isomerization in DMF. For dioxane and NHC situation, in the presence of neutral NHC ligand, the -PO 4 Et 2 group tightly coordinates with the Cu center after the oxidative addition, preventing the isomerization process. The regioselectivity is determined by the relative facility of the oxidative addition step. Therefore, the favorable oxidative addition (in which -CH 2 Bpin trans to the leaving group) results in the facility of γ-alkylation.

  7. Tripodal (N-alkylated) CMP(O) and malonamide ligands: synthesis, extraction of metal ions, and potentiometric studies

    Energy Technology Data Exchange (ETDEWEB)

    Janczewski, D.; Reinhoudt, D.N.; Verboom, W. [Twente Univ., Lab. of Supramolecular Chemistry and Technology, Mesa Research Institute for Nanotechnology, Enschede (Netherlands); Malinowska, E.; Pietrzak, M. [Warsaw Univ. of Technology, Dept. of Analytical Chemistry, Faculty of Chemistry (Poland); Hill, C.; Allignol, C. [CEA Valrho, 30 - Marcoule (France)

    2007-01-15

    Tripodal ligands build on the C-pivot (9b-e, 13b-d, and 17a-d) and tri-alkyl-benzene platforms (10a,b, 11, 12, 14a,b, and 18a,b) bearing (N-alkylated) carbamoyl-methyl-phosphine oxide (CMPO), carbamoyl-methyl-phosphonate (CMP), and malonamide moieties were synthesized. Extraction studies with Am{sup 3+} and Eu{sup 3+} show that in general there is a positive influence of the N-alkyl substituents in C-pivot CMP(O) ligands on the D(distribution) coefficients. The tri-alkyl-benzene CMPO ligands 10a,b, 11, and 12 have considerably larger D coefficients than the corresponding C-pivot analogues 9a-e, although hardly having any selectivity, while N-alkylation gives rise to smaller D coefficients. Although less effective the extraction behavior of the C-pivot CMP analogues 13b-d shows more or less the same trend as the corresponding CMPO ligands 9b-e upon substitution of the carboxamide N-atom with different alkyl chains. The different malonamide ligands 17a-d and 18a,b are bad extractants, while N-alkylation makes them even worse. Potentiometric studies of CMP(O) and malonamide ligands in polymeric membranes on Pb{sup 2+}, Cu{sup 2+}, Ca{sup 2+}, Mg{sup 2+}, Na{sup +}, and K{sup +} salts revealed that N-alkyl substituents increase the stability constants of ion-ionophore complexes compared to unsubstituted ligands. In polymeric membrane electrodes the ligands induce a selectivity pattern that differs significantly from the so-called Hofmeister series, giving the highest selectivity coefficients for UO{sub 2}{sup 2+} among all examined cations (Pb{sup 2+}, Cu{sup 2+}, Ca{sup 2+}, Mg{sup 2+}, Na{sup +}, K{sup +}). (authors)

  8. Kinetics of silica-phase transitions

    International Nuclear Information System (INIS)

    Duffy, C.J.

    1993-07-01

    In addition to the stable silica polymorph quartz, several metastable silica phases are present in Yucca Mountain. The conversion of these phases to quartz is accompanied by volume reduction and a decrease in the aqueous silica activity, which may destabilize clinoptilolite and mordenite. The primary reaction sequence for the silica phases is from opal or glass to disordered opal-CT, followed by ordering of the opal-CT and finally by the crystallization of quartz. The ordering of opal-CT takes place in the solid state, whereas the conversion of opal-CT takes place through dissolution-reprecipitation involving the aqueous phase. It is proposed that the rate of conversion of opal-CT to quartz is controlled by diffusion of defects out of a disordered surface layer formed on the crystallizing quartz. The reaction rates are observed to be dependent on temperature, pressure, degree of supersaturation, and pH. Rate equations selected from the literature appear to be consistent with observations at Yucca Mountain

  9. Determination of Alkyl Esters Content in PDO Extra Virgin Olive Oils from Sicily

    Directory of Open Access Journals (Sweden)

    Rosaria Costa

    2017-01-01

    Full Text Available The quality parameter of alkyl esters of fatty acids was checked in a variety of Italian olive oil samples. In particular, 34 samples of extra virgin olive oils (EVOOs from South Italy (Sicilian orchards, produced in the years 2014-2015, have been subjected to the analytical protocol dictated by the European Union for the determination of alkyl esters, as an indicator of oil’s quality. All the samples analyzed resulted to be well below the limit set by EU Directive. Besides recently produced EVOOs, a set of very aged oils, produced in the years 1996–2000, were analyzed as well. The main finding was that alkyl esters increased in correspondence with deterioration processes.

  10. Health hazards due to the inhalation of amorphous silica

    Energy Technology Data Exchange (ETDEWEB)

    Merget, R.; Bruening, T. [Research Institute for Occupational Medicine (BGFA), Bochum (Germany); Bauer, T. [Bergmannsheil, University Hospital, Department of Internal Medicine, Division of Pneumonology, Allergology and Sleep Medicine, Bochum (Germany); Kuepper, H.U.; Breitstadt, R. [Degussa-Huels Corp., Wesseling (Germany); Philippou, S. [Department of Pathology, Augusta Krankenanstalten, Bochum (Germany); Bauer, H.D. [Research Institute for Hazardous Substances (IGF), Bochum (Germany)

    2002-01-01

    Occupational exposure to crystalline silica dust is associated with an increased risk for pulmonary diseases such as silicosis, tuberculosis, chronic bronchitis, chronic obstructive pulmonary disease (COPD) and lung cancer. This review summarizes the current knowledge about the health effects of amorphous (non-crystalline) forms of silica. The major problem in the assessment of health effects of amorphous silica is its contamination with crystalline silica. This applies particularly to well-documented pneumoconiosis among diatomaceous earth workers. Intentionally manufactured synthetic amorphous silicas are without contamination of crystalline silica. These synthetic forms may be classified as (1) wet process silica, (2) pyrogenic (''thermal'' or ''fumed'') silica, and (3) chemically or physically modified silica. According to the different physico-chemical properties, the major classes of synthetic amorphous silica are used in a variety of products, e.g. as fillers in the rubber industry, in tyre compounds, as free-flow and anti-caking agents in powder materials, and as liquid carriers, particularly in the manufacture of animal feed and agrochemicals; other uses are found in toothpaste additives, paints, silicon rubber, insulation material, liquid systems in coatings, adhesives, printing inks, plastisol car undercoats, and cosmetics. Animal inhalation studies with intentionally manufactured synthetic amorphous silica showed at least partially reversible inflammation, granuloma formation and emphysema, but no progressive fibrosis of the lungs. Epidemiological studies do not support the hypothesis that amorphous silicas have any relevant potential to induce fibrosis in workers with high occupational exposure to these substances, although one study disclosed four cases with silicosis among subjects exposed to apparently non-contaminated amorphous silica. Since the data have been limited, a risk of chronic bronchitis, COPD or

  11. Health hazards due to the inhalation of amorphous silica

    International Nuclear Information System (INIS)

    Merget, R.; Bruening, T.; Bauer, T.; Kuepper, H.U.; Breitstadt, R.; Philippou, S.; Bauer, H.D.

    2002-01-01

    Occupational exposure to crystalline silica dust is associated with an increased risk for pulmonary diseases such as silicosis, tuberculosis, chronic bronchitis, chronic obstructive pulmonary disease (COPD) and lung cancer. This review summarizes the current knowledge about the health effects of amorphous (non-crystalline) forms of silica. The major problem in the assessment of health effects of amorphous silica is its contamination with crystalline silica. This applies particularly to well-documented pneumoconiosis among diatomaceous earth workers. Intentionally manufactured synthetic amorphous silicas are without contamination of crystalline silica. These synthetic forms may be classified as (1) wet process silica, (2) pyrogenic (''thermal'' or ''fumed'') silica, and (3) chemically or physically modified silica. According to the different physico-chemical properties, the major classes of synthetic amorphous silica are used in a variety of products, e.g. as fillers in the rubber industry, in tyre compounds, as free-flow and anti-caking agents in powder materials, and as liquid carriers, particularly in the manufacture of animal feed and agrochemicals; other uses are found in toothpaste additives, paints, silicon rubber, insulation material, liquid systems in coatings, adhesives, printing inks, plastisol car undercoats, and cosmetics. Animal inhalation studies with intentionally manufactured synthetic amorphous silica showed at least partially reversible inflammation, granuloma formation and emphysema, but no progressive fibrosis of the lungs. Epidemiological studies do not support the hypothesis that amorphous silicas have any relevant potential to induce fibrosis in workers with high occupational exposure to these substances, although one study disclosed four cases with silicosis among subjects exposed to apparently non-contaminated amorphous silica. Since the data have been limited, a risk of chronic bronchitis, COPD or emphysema cannot be excluded. There is no

  12. Amphetamine in rat brain after intraperitoneal injection of N-alkylated analogues.

    Science.gov (United States)

    Nazarali, A J; Baker, G B; Coutts, R T; Pasutto, F M

    1983-01-01

    Three N-alkylated analogues of amphetamine were administered intraperitoneally to male Sprague-Dawley rats and whole brain levels of amphetamine (AM) and the N-alkyl analogue were determined one hour after injection of the N-alkylated compounds. The drugs administered were the N-2-cyanoethyl-(I) (fenproporex), the N-3-chloropropyl-(II) (mefenorex) and the N-n-propyl-(III) derivatives of AM: the first two of these are used clinically as anorexiants, and the latter has been used extensively to study aspects of metabolism of AM-like compounds. Analysis of AM, I, II and III was performed using electron-capture gas chromatography with a capillary column after reaction of compounds with pentafluorobenzoyl chloride under aqueous conditions. In a second comparative study, equimolar doses (0.05 mMole/kg) of I or AM were administered intraperitoneally to the rats and brain levels determined after one hour. Results indicate extensive N-dealkylation occurs for compounds I, II and III in the rat.

  13. Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines.

    Science.gov (United States)

    Ikawa, Takashi; Fujita, Yuki; Mizusaki, Tomoteru; Betsuin, Sae; Takamatsu, Haruki; Maegawa, Tomohiro; Monguchi, Yasunari; Sajiki, Hironao

    2012-01-14

    Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.

  14. Biodesulfurization of dibenzothiophene and its alkylated derivatives ...

    African Journals Online (AJOL)

    RIPI-S81 is a new dibenzothiophene (DBT)-desulfurizing bacterium, which was isolated by Research Institute of Petroleum Industry in Iran. Resting cells and growing cells of RIPI-S81 was able to convert alkylated dibenzothiophenes (Cx DBTs) to hydroxybiphenyls such that they were almost stoichiometrically accumulated ...

  15. Grassy Silica Nanoribbons and Strong Blue Luminescence

    Science.gov (United States)

    Wang, Shengping; Xie, Shuang; Huang, Guowei; Guo, Hongxuan; Cho, Yujin; Chen, Jun; Fujita, Daisuke; Xu, Mingsheng

    2016-09-01

    Silicon dioxide (SiO2) is one of the key materials in many modern technological applications such as in metal oxide semiconductor transistors, photovoltaic solar cells, pollution removal, and biomedicine. We report the accidental discovery of free-standing grassy silica nanoribbons directly grown on SiO2/Si platform which is commonly used for field-effect transistors fabrication without other precursor. We investigate the formation mechanism of this novel silica nanostructure that has not been previously documented. The silica nanoribbons are flexible and can be manipulated by electron-beam. The silica nanoribbons exhibit strong blue emission at about 467 nm, together with UV and red emissions as investigated by cathodoluminescence technique. The origins of the luminescence are attributed to various defects in the silica nanoribbons; and the intensity change of the blue emission and green emission at about 550 nm is discussed in the frame of the defect density. Our study may lead to rational design of the new silica-based materials for a wide range of applications.

  16. Characterization of silica particles prepared via urease-catalyzed urea hydrolysis and activity of urease in sol–gel silica matrix

    International Nuclear Information System (INIS)

    Kato, Katsuya; Nishida, Masakazu; Ito, Kimiyasu; Tomita, Masahiro

    2012-01-01

    Highlights: ► Silica precipitation occurred via urease-catalytic reactions. ► Higher urease activity for silica synthesis enables mesostructure of silica–urease composites. ► Urease encapsulating in silica matrix retained high activity. - Abstract: Urease templated precipitation of silica synthesized by sol–gel chemistry produces a composite material allowing high urease activity. This study investigates the structural properties of the composite material that allow for the retention of the urease hydrolysis activity. Scanning (SEM) and transmission (TEM) electron microscopy reveal that the composite has a mesoporous structure composed of closely packed spherical structures ∼20–50 nm in diameter. Brunauer–Emmett–Teller (BET) analysis revealed that the surface area and pore volume of the composite prepared under the conditions of 50 mM urea and 25 °C is relatively high (324 m 2 /g and 1.0 cm 3 /g). These values are equivalent to those of usual mesoporous silica materials synthesized from the self-assembly of triblock copolymers as organic templates. In addition, after encapsulating in a sol–gel silica matrix, urease retained high activity (∼90% of the activity compared with native urease). Our results suggest a new method for synthesizing mesoporous silica materials with highly tunable pore sizes and shapes under mild conditions.

  17. SERIES: Genomic instability in cancer Balancing repair and tolerance of DNA damage caused by alkylating agents

    OpenAIRE

    Fu, Dragony; Calvo, Jennifer A.; Samson, Leona D

    2012-01-01

    Alkylating agents comprise a major class of frontline chemotherapeutic drugs that inflict cytotoxic DNA damage as their main mode of action, in addition to collateral mutagenic damage. Numerous cellular pathways, including direct DNA damage reversal, base excision repair (BER), and mismatch repair (MMR) respond to alkylation damage to defend against alkylation-induced cell death or mutation. However, maintaining a proper balance of activity both within and between these pathways is crucial fo...

  18. Hydration of urea and alkylated urea derivatives

    Science.gov (United States)

    Kaatze, Udo

    2018-01-01

    Compressibility data and broadband dielectric spectra of aqueous solutions of urea and some of its alkylated derivatives have been evaluated to yield their numbers Nh of hydration water molecules per molecule of solute. Nh values in a broad range of solute concentrations are discussed and are compared to hydration numbers of other relevant molecules and organic ions. Consistent with previous results, it is found that urea differs from other solutes in its unusually small hydration number, corresponding to just one third of the estimated number of nearest neighbor molecules. This remarkable hydration behavior is explained by the large density φH of hydrogen bonding abilities offered by the urea molecule. In terms of currently discussed models of reorientational motions and allied dynamics in water and related associating liquids, the large density φH causes a relaxation time close to that of undisturbed water with most parts of water encircling the solute. Therefore only a small part of disturbed ("hydration") water is left around each urea molecule. Adding alkyl groups to the basic molecule leads to Nh values which, within the series of n-alkylurea derivatives, progressively increase with the number of methyl groups per solute. With n-butylurea, Nh from dielectric spectra, in conformity with many other organic solutes, slightly exceeds the number of nearest neighbors. Compared to such Nh values, hydration numbers from compressibility data are substantially smaller, disclosing incorrect assumptions in the formula commonly used to interpret the experimental compressibilities. Similar to other series of organic solutes, effects of isomerization have been found with alkylated urea derivatives, indicating that factors other than the predominating density φH of hydrogen bond abilities contribute also to the hydration properties.

  19. Winter climate change and fine root biogenic silica in sugar maple trees (Acer saccharum): Implications for silica in the Anthropocene

    Science.gov (United States)

    Maguire, Timothy J.; Templer, Pamela H.; Battles, John J.; Fulweiler, Robinson W.

    2017-03-01

    Winter temperatures are projected to increase over the next century, leading to reductions in winter snowpack and increased frequency of soil freezing in many northern forest ecosystems. Here we examine biogenic silica (BSi) concentrations in sugar maple (Acer saccharum) fine roots collected from a snow manipulation experiment at Hubbard Brook Experimental Forest (New Hampshire, USA). Increased soil freezing significantly lowered the BSi content of sugar maple fine roots potentially decreasing their capacity to take up water and dissolved nutrients. The reduced silica uptake (8 ± 1 kmol silica km-2) by sugar maple fine roots is comparable to silica export from temperate forest watersheds. We estimate that fine roots account for 29% of sugar maple BSi, despite accounting for only 4% of their biomass. These results suggest that increased frequency of soil freezing will reduce silica uptake by temperate tree roots, thereby changing silica availability in downstream receiving waters.

  20. Mesoporous Silica from Rice Husk Ash

    Directory of Open Access Journals (Sweden)

    V.R. Shelke

    2011-01-01

    Full Text Available Mesoporous silica is used as a raw material in several areas: in preparation of catalysts, in inks, as a concrete hardening accelerator, as a component of detergents and soaps, as a refractory constituent etc. Sodium silicate is produced by reacting rice hull ash (RHA with aqueous NaOH and silica is precipitated from the sodium silicate by acidification. In the present work, conversion of about 90% of silica contained in RHA into sodium silicate was achieved in an open system at temperatures of about 100 °C. The results showed that silica obtained from RHA is mesoporous, has a large surface area and small particle size. Rice Husk is usually mixed with coal and this mixture is used for firing boilers. The RHA therefore, usually contains carbon particles. Activated carbon embedded on silica has been prepared using the carbon already present in RHA. This carbon shows good adsorption capacity. ©2010 BCREC UNDIP. All rights reserved(Received: 25th April 2010, Revised: 17th June 2010, Accepted: 24th June 2010[How to Cite: V.R. Shelke, S.S. Bhagade, S.A. Mandavgane. (2010. Mesoporous Silica from Rice Husk Ash. Bulletin of Chemical Reaction Engineering and Catalysis, 5 (2: 63-67. doi:10.9767/bcrec.5.2.793.63-67][DOI: http://dx.doi.org/10.9767/bcrec.5.2.793.63-67

  1. Production and Application of Olivine Nano-Silica in Concrete

    Science.gov (United States)

    Mardiana, Oesman; Haryadi

    2017-05-01

    The aim of this research was to produce nano silica by synthesis of nano silica through extraction and dissolution of ground olivine rock, and applied the nano silica in the design concrete mix. The producing process of amorphous silica used sulfuric acid as the dissolution reagent. The separation of ground olivine rock occurred when the rock was heated in a batch reactor containing sulfuric acid. The results showed that the optimum mole ratio of olivine- acid was 1: 8 wherein the weight ratio of the highest nano silica generated. The heating temperature and acid concentration influenced the mass of silica produced, that was at temperature of 90 °C and 3 M acid giving the highest yield of 44.90%. Characterization using Fourier Transform Infrared (FTIR ) concluded that amorphous silica at a wavenumber of 1089 cm-1 indicated the presence of siloxane, Si-O-Si, stretching bond. Characterization using Scanning Electron Microscope - Energy Dispersive Spectroscopy (SEM-EDS) showed the surface and the size of the silica particles. The average size of silica particles was between 1-10 μm due to the rapid aggregation of the growing particles of nano silica into microparticles, caused of the pH control was not fully achieved.

  2. Ada response – a strategy for repair of alkylated DNA in bacteria

    Science.gov (United States)

    Mielecki, Damian; Grzesiuk, Elżbieta

    2014-01-01

    Alkylating agents are widespread in the environment and also occur endogenously. They can be cytotoxic or mutagenic to the cells introducing alkylated bases to DNA or RNA. All organisms have evolved multiple DNA repair mechanisms to counteract the effects of DNA alkylation: the most cytotoxic lesion, N3-methyladenine (3meA), is excised by AlkA glycosylase initiating base excision repair (BER); toxic N1-methyladenine (1meA) and N3-methylcytosine (3meC), induced in DNA and RNA, are removed by AlkB dioxygenase; and mutagenic and cytotoxic O6-methylguanine (O6meG) is repaired by Ada methyltransferase. In Escherichia coli, Ada response involves the expression of four genes, ada, alkA, alkB, and aidB, encoding respective proteins Ada, AlkA, AlkB, and AidB. The Ada response is conserved among many bacterial species; however, it can be organized differently, with diverse substrate specificity of the particular proteins. Here, an overview of the organization of the Ada regulon and function of individual proteins is presented. We put special effort into the characterization of AlkB dioxygenases, their substrate specificity, and function in the repair of alkylation lesions in DNA/RNA. PMID:24810496

  3. Phase behavior for the poly(alkyl methacrylate)+supercritical CO2+DME mixture at high pressures

    International Nuclear Information System (INIS)

    Choi, Yong-Seok; Chio, Sang-Won; Byun, Hun-Soo

    2016-01-01

    The phase behavior curves of binary and ternary system were measured for poly(alkyl methacrylate) in supercritical CO 2 , as well as for the poly(alkyl methacrylate)+dimethyl ether (DME) (or 1-butene) in CO 2 . The solubility curves are reported for the poly(alkyl methacrylate)+DME in supercritical CO 2 at temperature from (300 to 465) K and a pressure from (3.66 to 248) MPa. Also, The high-pressure static-type apparatus of cloud-point curve was tested by comparing the measured phase behavior data of the poly(methyl methacrylate) [PMMA]+CO 2 +20.0 and 30.4 wt% methyl methacrylate (MMA) system with literature data of 10.4, 28.8 and 48.4 wt% MMA concentration. The phase behavior data for the poly(alkyl methacrylate)+CO 2 +DME mixture were measured in changes of the pressure-temperature (p, T) slope and with DME concentrations. Also, the cloud-point pressure for the poly(alkyl methacrylate)+1- butene solution containing supercritical CO 2 shows from upper critical solution temperature (UCST) region to lower critical solution temperature (LCST) region at concentration range from (0.0 to 95) wt% 1-butene at below 455 K and at below 245MPa.

  4. Rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides: is solute rotation always influenced by the length of the alkyl chain on the imidazolium cation?

    Science.gov (United States)

    Gangamallaiah, V; Dutt, G B

    2012-10-25

    In an attempt to find out whether the length of the alkyl chain on the imidazolium cation has a bearing on solute rotation, temperature-dependent fluorescence anisotropies of three structurally similar solutes have been measured in a series of 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides. Solute-solvent coupling constants obtained from the experimentally measured reorientation times with the aid of Stokes-Einstein-Debye hydrodynamic theory indicate that there is no influence of the length of the alkyl chain on the rotation of nonpolar, anionic, and cationic solutes 9-phenylanthracene (9-PA), fluorescein (FL), and rhodamine 110 (R110), respectively. It has also been noticed that the rotational diffusion of 9-PA is closer to the predictions of slip hydrodynamics, whereas the rotation of negatively charged FL and positively charged R110 is almost identical and follows stick hydrodynamics in these ionic liquids. Despite having similar shape and size, ionic solutes rotate slower by a factor of 3-4 compared to the nonpolar solute. Interplay of specific and electrostatic interactions between FL and the imidazolium cation of the ionic liquids, and between R110 and the bis(trifluoromethylsulfonyl)imide anion, appear to be responsible for the observed behavior. These results are an indication that the length of the alkyl chain on the imidazolium cation does not alter their physical properties in a manner that has an effect on solute rotation.

  5. Synthesis of 2-substituted tryptophans via a C3- to C2-alkyl migration

    Directory of Open Access Journals (Sweden)

    Michele Mari

    2014-08-01

    Full Text Available The reaction of 3-substituted indoles with dehydroalanine (Dha derivatives under Lewis acid-mediated conditions has been investigated. The formation of 2-substituted tryptophans is proposed to occur through a selective alkylative dearomatization–cyclization followed by C3- to C2-alkyl migration and rearomatization.

  6. Pumping Iron and Silica Bodybuilding

    Science.gov (United States)

    Mcnair, H.; Brzezinski, M. A.; Krause, J. W.; Parker, C.; Brown, M.; Coale, T.; Bruland, K. W.

    2016-02-01

    The availability of dissolved iron influences the stoichiometry of nutrient uptake by diatoms. Under nutrient replete conditions diatoms consume silicic acid and nitrate in a 1:1 ratio, this ratio increases under iron stress. Using the tracers 32Si and PDMPO, the total community and group-specific silica production rates were measured along a gradient of dissolved iron in an upwelling plume off the California coast. At each station, a control (ambient silicic acid) and +20 µM silicic acid treatment were conducted with each tracer to determine whether silicic acid limitation controlled the rate of silica production. Dissolved iron was 1.3 nmol kg-1 nearshore and decreased to 0.15 nmol kg-1 offshore. Silicic acid decreased more rapidly than nitrate, it was nearly 9 µM higher in the nearshore and 7 µM lower than nitrate in the middle of the transect where the iron concentration had decreased. The rate of diatom silica production decreased in tandem with silicic acid concentration, and silica production limitation by low silicic acid was most pronounced when iron concentrations were >0.4 nmol kg-1. The composition of the diatom assemblage shifted from Chaetoceros spp. dominated nearshore to a more sparse pennate-dominated assemblage offshore. Changes in taxa-specific silica production rates will be reported based on examination of PDMPO labeled cells using confocal microscopy.

  7. Nitric oxide donors attenuate clongenic potential in rat C6 glioma cells treated with alkylating chemotherapeutic agents.

    Science.gov (United States)

    Yang, Jir-Jei; Yin, Jiu-Haw; Yang, Ding-I

    2007-05-11

    1,3-Bis(2-chloroethyl)-1-nitrosourea (BCNU) kills tumor cells via multiple actions including alkylation and carbamoylation. Previously, we have reported that formation of S-nitrosoglutathione (GSNO) in glioma cells overexpressing inducible nitric oxide synthase (iNOS) contributed to nitric oxide (NO)-dependent carbamoylating chemoresistance against BCNU. To further characterize the effects of NO on alkylating cytotoxicity, colony formation assay was applied to evaluate the effects of various NO donors on rat C6 glioma cells challenged with alkylating agents. We demonstrate that NO donors including GSNO, diethylamine NONOate (DEA/NO), and sodium nitroprusside (SNP) substantially reduced the extent of colony formation in glioma cells treated with alkylating agents, namely methyl methanesulfonate (MMS), N-methyl-N-nitrosourea (MNU), and N-ethyl-N-nitrosourea (ENU). Without alkylating agents these NO-releasing agents alone had no effects on clongenic potential of rat C6 glioma cells. Among these three NO donors used, the effectiveness in potentiating alkylating cytotoxicity is in the order of "GSNO>DEA/NO>SNP" when applied at the same dosages. GSNO also exerted similar synergistic actions reducing the extents of colony formation when co-administrated with 1,2-bis(methylsulfonyl)-1-(2-chloroethyl)-hydrazine (compound #1), another alkylating agent that mimics the chloroethylating action of BCNU. Together with our previous findings, we propose that NO donors may be used as adjunct chemotherapy with alkylating agents for such malignant brain tumors as glioblastoma multiforme (GBM). In contrast, production of NO as a result of iNOS induction, such as that occurring after surgical resection of brain tumors, may compromise the efficacy of carbamoylating chemotherapy.

  8. Alkylating agent (MNU)-induced mutation in space environment

    Science.gov (United States)

    Ohnishi, T.; Takahashi, A.; Ohnishi, K.; Takahashi, S.; Masukawa, M.; Sekikawa, K.; Amano, T.; Nakano, T.; Nagaoka, S.

    2001-01-01

    In recent years, some contradictory data about the effects of microgravity on radiation-induced biological responses in space experiments have been reported. We prepared a damaged template DNA produced with an alkylating agent (N-methyl-N-nitroso urea; MNU) to measure incorrect base-incorporation during DNA replication in microgravity. We examined whether mutation frequency is affected by microgravity during DNA replication for a DNA template damaged by an alkylating agent. Using an in vitro enzymatic reaction system, DNA synthesis by Taq polymerase or polymerase III was done during a US space shuttle mission (Discovery, STS-91). After the flight, DNA replication and mutation frequencies were measured. We found that there was almost no effect of microgravity on DNA replication and mutation frequency. It is suggested that microgravity might not affect at the stage of substrate incorporation in induced-mutation frequency.

  9. Influence of diluent alkyl substitution on the extraction of Am(III) and Eu(III) by a 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine ligand dissolved in alkylated cyclohexanone diluents

    International Nuclear Information System (INIS)

    Distler, P.; Spendlikova, I.; John, J.; Czech Technical Univ., Prague; Harwood, L.M.; Hudson, M.J.; Lewis, F.W.

    2012-01-01

    Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) from Eu(III) from nitric acid solutions by the CyMe 4 -BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO 3 , 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO 3 , 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, D Am and SF Am/Eu decreased in the order of alkyl substitution 2 > 4 ∝ 3. However, alkyl substitution of cyclohexanone significantly slows down the extraction kinetics compared to cyclohexanone, and the position of alkyl substitution was found to play an important role in the solvents properties. 3-Methylcyclohexanone was identified as the most promising of the diluents. (orig.)

  10. Sequence-specific DNA alkylation targeting for Kras codon 13 mutation by pyrrole-imidazole polyamide seco-CBI conjugates.

    Science.gov (United States)

    Taylor, Rhys Dylan; Asamitsu, Sefan; Takenaka, Tomohiro; Yamamoto, Makoto; Hashiya, Kaori; Kawamoto, Yusuke; Bando, Toshikazu; Nagase, Hiroki; Sugiyama, Hiroshi

    2014-01-27

    Hairpin N-methylpyrrole-N-methylimidazole polyamide seco-CBI conjugates 2-6 were designed for synthesis by Fmoc solid-phase synthesis, and their DNA-alkylating activities against the Kras codon 13 mutation were compared by high-resolution denaturing gel electrophoresis with 225 base pair (bp) DNA fragments. Conjugate 5 had high reactivity towards the Kras codon 13 mutation site, with alkylation occurring at the A of the sequence 5'-ACGTCACCA-3' (site 2), including minor 1 bp-mismatch alkylation against wild type 5'-ACGCCACCA-3' (site 3). Conjugate 6, which differs from conjugate 5 by exchanging one Py unit with a β unit, showed high selectivity but only weakly alkylated the A of 5'-ACGTCACCA-3' (site 2). The hairpin polyamide seco-CBI conjugate 5 thus alkylates according to Dervan's pairing rule with the pairing recognition which β/β pair targets T-A and A-T pairs. SPR and a computer-minimized model suggest that 5 binds to the target sequence with high affinity in a hairpin conformation, allowing for efficient DNA alkylation. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Effect of silica particle size on macrophage inflammatory responses.

    Directory of Open Access Journals (Sweden)

    Toshimasa Kusaka

    Full Text Available Amorphous silica particles, such as nanoparticles (<100 nm diameter particles, are used in a wide variety of products, including pharmaceuticals, paints, cosmetics, and food. Nevertheless, the immunotoxicity of these particles and the relationship between silica particle size and pro-inflammatory activity are not fully understood. In this study, we addressed the relationship between the size of amorphous silica (particle dose, diameter, number, and surface area and the inflammatory activity (macrophage phagocytosis, inflammasome activation, IL-1β secretion, cell death and lung inflammation. Irrespective of diameter size, silica particles were efficiently internalized by mouse bone marrow-derived macrophages via an actin cytoskeleton-dependent pathway, and induced caspase-1, but not caspase-11, activation. Of note, 30 nm-1000 nm diameter silica particles induced lysosomal destabilization, cell death, and IL-1β secretion at markedly higher levels than did 3000 nm-10000 nm silica particles. Consistent with in vitro results, intra-tracheal administration of 30 nm silica particles into mice caused more severe lung inflammation than that of 3000 nm silica particles, as assessed by measurement of pro-inflammatory cytokines and neutrophil infiltration in bronchoalveolar lavage fluid of mice, and by the micro-computed tomography analysis. Taken together, these results suggest that silica particle size impacts immune responses, with submicron amorphous silica particles inducing higher inflammatory responses than silica particles over 1000 nm in size, which is ascribed not only to their ability to induce caspase-1 activation but also to their cytotoxicity.

  12. Pecan drying with silica gel

    Energy Technology Data Exchange (ETDEWEB)

    Ghate, S.R.; Chhinnan, M.S.

    1983-07-01

    High moisture in-shell pecans were dried by keeping them in direct and indirect contact with silica gel to investigate their drying characteristics. In-shell pecans were also dried with ambient air from a controlled environment chamber and with air dehumidified by silica gel. Direct contact and dehumidified air drying seemed feasible approaches.

  13. DNA alkylation damage as a sensor of nitrosative stress in Mycobacterium tuberculosis

    OpenAIRE

    Durbach, S I; Springer, B; Machowski, E E; North, R J; Papavinasasundaram, K G; Colston, M J; Böttger, E C; Mizrahi, V

    2003-01-01

    One of the cellular consequences of nitrosative stress is alkylation damage to DNA. To assess whether nitrosative stress is registered on the genome of Mycobacterium tuberculosis, mutants lacking an alkylation damage repair and reversal operon were constructed. Although hypersensitive to the genotoxic effects of N-methyl-N′-nitro-N-nitrosoguanidine in vitro, the mutants displayed no phenotype in vivo, suggesting that permeation of nitrosative stress to the level of cytotoxic DNA damage is res...

  14. Metal halide-phosphorus halide-alkyl halide complexes: reaction with niobium and tantalum pentachlorides

    International Nuclear Information System (INIS)

    Puri, D.M.; Saini, M.S.

    1978-01-01

    The reactions of niobium and tantalum pentachlorides with trichlorophosphine and phenyldichlorophosphine have been studied in presence of alkylating agents such as sec-butyl chloride, iso-butyl chloride, tert-butyl chloride, tert-anylchloride, cyclohexyl chloride and triphenylmethyl chloride. Solid products have been isolated and characterised by vibrational spectroscopy as ionic complexes of alkyl- and/or aryl-phosphonium cations with hexachloroniobate and hexachlorotantalate anions. (author)

  15. 46 CFR 153.560 - Special requirements for Alkyl (C7-C9) nitrates.

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Special requirements for Alkyl (C7-C9) nitrates. 153.560... Equipment Special Requirements § 153.560 Special requirements for Alkyl (C7-C9) nitrates. (a) The carriage temperature of octyl nitrates must be maintained below 100 °C (212 °F) in order to prevent the occurrence of a...

  16. Influence of organic solvents on interfacial water at surfaces of silica gel and partially silylated fumed silica

    International Nuclear Information System (INIS)

    Turov, V.V.; Gun'ko, V.M.; Tsapko, M.D.; Bogatyrev, V.M.; Skubiszewska-Zieba, J.; Leboda, R.; Ryczkowski, J.

    2004-01-01

    The effects of organic solvents (dimethylsulfoxide-d 6 (DMSO-d 6 ), chloroform-d, acetone-d 6 , and acetonitrile-d 3 ) on the properties of interfacial water at surfaces of silica gel Si-40 and partially silylated fumed silica A-380 were studied by means of the 1 H NMR spectroscopy with freezing-out of adsorbed water at 180 1 H NMR investigations were also analysed on the basis of the structural characteristics of silicas and quantum chemical calculations of the chemical shifts δ H and solvent effects. DMSO-d 6 and acetonitrile-d 3 are poorly miscible with water in silica gel pores in contrast to the bulk liquids. DMSO-d 6 and chloroform-d affect the structure of the interfacial water weaker than acetone-d 6 and acetonitrile-d 3 at amounts of liquids greater than the pore volume. Acetone-d 6 and acetonitrile-d 3 can displace water from pores under this condition. The chemical shift of protons in water adsorbed on silica gel is 3.5-6.5 ppm, which corresponds to the formation of two to four hydrogen bonds per molecule. Water adsorbed on partially silylated fumed silica has two 1 H NMR signals at 5 and 1.1-1.7 ppm related to different structures (droplets and small clusters) of the interfacial water

  17. Silica and lung cancer: a controversial issue.

    Science.gov (United States)

    Pairon, J C; Brochard, P; Jaurand, M C; Bignon, J

    1991-06-01

    The role of crystalline silica in lung cancer has long been the subject of controversy. In this article, we review the main experimental and epidemiological studies dealing with this problem. Some evidence for a genotoxic potential of crystalline silica has been obtained in the rare in vitro studies published to date. In vivo studies have shown that crystalline silica is carcinogenic in the rat; the tumour types appear to vary according to the route of administration. In addition, an association between carcinogenic and fibrogenic potency has been observed in various animal species exposed to crystalline silica. An excess of lung cancer related to occupational exposure to crystalline silica is reported in many epidemiological studies, regardless of the presence of silicosis. However, most of these studies are difficult to interpret because they do not correctly take into account associated carcinogens such as tobacco smoke and other occupational carcinogens. An excess of lung cancer is generally reported in studies based on silicosis registers. Overall, experimental and human studies suggest an association between exposure to crystalline silica and an excess of pulmonary malignancies. Although the data available are not sufficient to establish a clear-cut causal relationship in humans, an association between the onset of pneumoconiosis and pulmonary malignancies is probable. In contrast, experimental observations have given rise to a pathophysiological mechanism that might account for a putative carcinogenic potency of crystalline silica.

  18. Selectivity of calixarene-bonded silica-phases in HPLC: description of special characteristics with a multiple term linear equation at two different pH-values.

    Science.gov (United States)

    Schneider, Christian; Meyer, Rüdiger; Jira, Thomas

    2008-09-01

    Six different calixarene-bonded phases were characterized by analyzing 36 and 26 solutes at pH 3 and 7, respectively. Dolan and Snyder's multiple term linear equation was used to correlate retention factors k' to parameters of the solutes and columns. The column parameters have been related to molecular properties of the stationary phases and new suggestions were made for the interpretation of steric selectivity. Ionic and polar interactions have been found dependent on pH value, while steric interactions are less dependent and hydrophobic interactions remain unchanged. Distinct differences of the supported interactions were confirmed between the calixarene-bonded and the common alkyl-bonded silicas. By use of the parameters, values of k' can be estimated with an average deviation of 2.50 and 7.92% at low and neutral pH-value, respectively.

  19. Rh(III-Catalyzed, Highly Selectively Direct C–H Alkylation of Indoles with Diazo Compounds

    Directory of Open Access Journals (Sweden)

    Kang Wan

    2016-06-01

    Full Text Available Rh(III-catalyzed regioselective alkylation of indoles with diazo compounds as a highly efficient and atom-economic protocol for the synthesis of alkyl substituted indoles has been developed. The reaction could proceed under mild conditions and afford a series of desired products in good to excellent yields.

  20. New Silica Magnetite Sorbent: The Influence of Variations of Sodium Silicate Concentrations on Silica Magnetite Character

    Science.gov (United States)

    Azmiyawati, C.; Pratiwi, P. I.; Darmawan, A.

    2018-04-01

    The adsorption capacity of an adsorbent is determined by the adsorbent and the adsorbate properties. The character of the adsorbent will play a major role in its ability to adsorb the corresponding adsorbate. Therefore, in this study we looked at the effects of variations of sodium silicate concentrations on the resulting magnetite silica adsorbent properties. The application of silica coating on the magnetite was carried out through a sol-gel process with sodium silicate and HCl precursors. Based on the characterization data obtained, it was found that the silica coating on magnetite can increase the resistance to acid leaching, increase the particle size, but decrease the magnetic properties of the magnetite. Based on Gas Sorption Analyzer (GSA) and X-ray Difraction (XRD) data it can successively be determined that increase in concentration of sodium silicate will increase the surface area and amorphous structure of the Silica Magnetie.

  1. Copper-Catalyzed Synthesis of Mixed Alkyl Aryl Phosphonates

    NARCIS (Netherlands)

    Fañanás-Mastral, Martín; Feringa, Ben L

    2014-01-01

    Copper-catalysis allows the direct oxygenarylation of dialkyl phosphonates with diaryliodonium salts. This novel methodology proceeds with a wide range of phosphonates and phosphoramidates under mild conditions and gives straightforward access to valuable mixed alkyl aryl phosphonates in very good

  2. Dispersibility of silica fume in mortar and its effect on properties of mortar. Silica fume no bunsan to mortar no shotokusei

    Energy Technology Data Exchange (ETDEWEB)

    Oga, H; Uomoto, T [The University of Tokyo, Tokyo (Japan). Institute of Industrial Science

    1992-08-01

    Effect of silica fume dispersibility on concrete characteristics was discussed. Properties of mortar mixed with silica fume to exhibit compression strength varied with displacement rates, patterns, and mixing time of silica fume. In submerged curing age of 28 days, the compression strength in a mortar mixed with silica fume at 10% was affected only very little by the mixing time for both pelletizing and non-pelletizing types for up to 180 seconds. The strength increased thereafter with the mixing time. The compression strength at 1020 seconds showed higher value by about 150 kgf/cm [sup 2] than when no silica fume is added, with a difference because of patterns disappearing. In the case of a mixing time of 1020 seconds, neutralization depth receives very little effect from a pattern difference, and decreases with increasing displacement rate. Neutralization coefficient of the mortar mixed with silica fume at 10% decreased with the mixing time, and it was possible to suppress the neutralization coefficient to 25% of the case without silica fume addition in a 1020-second mixing. 7 refs., 8 figs., 1 tab.

  3. Synthesis of Silica Nanoparticles by Sol-Gel: Size-Dependent Properties, Surface Modification, and Applications in Silica-Polymer Nano composites-A Review

    International Nuclear Information System (INIS)

    Ismail, A.R.; Vejayakumaran, P.

    2012-01-01

    Application of silica nanoparticles as fillers in the preparation of nano composite of polymers has drawn much attention, due to the increased demand for new materials with improved thermal, mechanical, physical, and chemical properties. Recent developments in the synthesis of monodispersed, narrow-size distribution of nanoparticles by sol-gel method provide significant boost to development of silica-polymer nano composites. This paper is written by emphasizing on the synthesis of silica nanoparticles, characterization on size-dependent properties, and surface modification for the preparation of homogeneous nano composites, generally by sol-gel technique. The effect of nano silica on the properties of various types of silica-polymer composites is also summarized.

  4. Effects of alkylating carcinogens on human tumor cells in culture

    International Nuclear Information System (INIS)

    Goth-Goldstein, R.; Hughes, M.

    1987-01-01

    In Escherichia coli 3-methyladenine and 3-methylguanine have been identified as lethal lesions, since two types of alkylating agent-sensitive mutants were deficient in repair of either of these lesions. Similar alkylation-sensitive human cell lines exist. These are the tumor cell lines of the complex Mer - phenotype. All Mer - cells examined were hypersensitive to killing by MNNG and other alkylating agents, and failed to repair O 6 -methylguanine. The widely studied HeLa S3 cell line has the Mer + phenotype, but a Mer - variant (HeLa MR) has arisen. This offers the possibility to study Mer - and Mer + cells of otherwise similar genetic background. We are using these two variants to analyze the Mer - phenotype further. When HeLa S3 and HeLa MR were treated with a highly dose of MNNG, and the surviving population exposed to a second dose of MNNG 2-3 weeks later, HeLa S3 (Mer + ) cells were equally or even slightly more sensitive to a second exposure of MNNG, whereas the surviving HeLa MR (Mer - ) population was much more resistant to MNNG. 1 fig., 1 tab

  5. Electronic Control on Linear versus Branched Alkylation of 2-/3-Aroylbenzofurans with Acrylates: Combined DFT and Synthetic Studies.

    Science.gov (United States)

    Srinivas, Kolluru; Dangat, Yuvraj; Kommagalla, Yadagiri; Vanka, Kumar; Ramana, Chepuri V

    2017-06-01

    Investigations on the factors that govern unusual branched alkylation of 2-aroylbenzofurans with acrylates by Ru-catalyzed carbonyl-directed C-H activation has been carried out by calculating the kinetics associated with the two key steps-the coordination of the acrylate with the intermediate ruthenacycle and the subsequent migratory insertion reaction-studied with the help of DFT calculations. Eight possible orientations for each mode of alkylation have been considered for the calculations. From these calculations, it has been understood that there is a synergistic operation of the steric and electronic effects favoring the branched alkylation. Further DFT investigations on the alkylation of the isomeric 3-aroylbenzofurans indicated a preference for the linear alkylation and this has been verified experimentally. Overall, the observed/calculated complementary selectivity in the alkylation of 2-/3-aroylbenzofurans with acrylates reveals that the substrate-dependent charge distribution of the Ru-C bond in the intermediate ruthenacycle is an important determining factor and thus the current work opens up a new domain of substrate design for controlling regioselectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Antibacterial activity of alkyl gallates is a combination of direct targeting of FtsZ and permeabilization of bacterial membranes

    NARCIS (Netherlands)

    Krol, Ewa; de Sousa Borges, Anabela; da Silva, Isabel; Polaquini, Carlos; Regasini, Luis; Ferreira, Henrique; Scheffers, Dirk

    2015-01-01

    Alkyl gallates are compounds with reported antibacterial activity. One of the modes of action is binding of the alkyl gallates to the bacterial membrane and interference with membrane integrity. However, alkyl gallates also cause cell elongation and disruption of cell division in the important plant

  7. Silica sol as grouting material: a physio-chemical analysis.

    Science.gov (United States)

    Sögaard, Christian; Funehag, Johan; Abbas, Zareen

    2018-01-01

    At present there is a pressing need to find an environmentally friendly grouting material for the construction of tunnels. Silica nanoparticles hold great potential of replacing the organic molecule based grouting materials currently used for this purpose. Chemically, silica nanoparticles are similar to natural silicates which are essential components of rocks and soil. Moreover, suspensions of silica nanoparticles of different sizes and desired reactivity are commercially available. However, the use of silica nanoparticles as grouting material is at an early stage of its technological development. There are some critical parameters such as long term stability and functionality of grouted silica that need to be investigated in detail before silica nanoparticles can be considered as a reliable grouting material. In this review article we present the state of the art regarding the chemical properties of silica nanoparticles commercially available, as well as experience gained from the use of silica as grouting material. We give a detailed description of the mechanisms underlying the gelling of silica by different salt solutions such as NaCl and KCl and how factors such as particle size, pH, and temperature affect the gelling and gel strength development. Our focus in this review is on linking the chemical properties of silica nanoparticles to the mechanical properties to better understand their functionality and stability as grouting material. Along the way we point out areas which need further research.

  8. Preparation of thick silica coatings on carbon fibers with fine-structured silica nanotubes induced by a self-assembly process

    Directory of Open Access Journals (Sweden)

    Benjamin Baumgärtner

    2017-05-01

    Full Text Available A facile method to coat carbon fibers with a silica shell is presented in this work. By immobilizing linear polyamines on the carbon fiber surface, the high catalytic activity of polyamines in the sol–gel-processing of silica precursors is used to deposit a silica coating directly on the fiber’s surface. The surface localization of the catalyst is achieved either by attaching short-chain polyamines (e.g., tetraethylenepentamine via covalent bonds to the carbon fiber surface or by depositing long-chain polyamines (e.g., linear poly(ethylenimine on the carbon fiber by weak non-covalent bonding. The long-chain polyamine self-assembles onto the carbon fiber substrate in the form of nanoscopic crystallites, which serve as a template for the subsequent silica deposition. The silicification at close to neutral pH is spatially restricted to the localized polyamine and consequently to the fiber surface. In case of the linear poly(ethylenimine, silica shells of several micrometers in thickness can be obtained and their morphology is easily controlled by a considerable number of synthesis parameters. A unique feature is the hierarchical biomimetic structure of the silica coating which surrounds the embedded carbon fiber by fibrillar and interconnected silica fine-structures. The high surface area of the nanostructured composite fiber may be exploited for catalytic applications and adsorption purposes.

  9. Ordered nanoporous silica as carriers for improved delivery of water insoluble drugs: a comparative study between three dimensional and two dimensional macroporous silica

    Directory of Open Access Journals (Sweden)

    Wang Y

    2013-10-01

    Full Text Available Ying Wang, Qinfu Zhao, Yanchen Hu, Lizhang Sun, Ling Bai, Tongying Jiang, Siling WangDepartment of Pharmaceutics, Shenyang Pharmaceutical University, Liaoning Province, People’s Republic of ChinaAbstract: The goal of the present study was to compare the drug release properties and stability of the nanoporous silica with different pore architectures as a matrix for improved delivery of poorly soluble drugs. For this purpose, three dimensional ordered macroporous (3DOM silica with 3D continuous and interconnected macropores of different sizes (200 nm and 500 nm and classic mesoporous silica (ie, Mobil Composition of Matter [MCM]-41 and Santa Barbara Amorphous [SBA]-15 with well-ordered two dimensional (2D cylindrical mesopores were successfully fabricated and then loaded with the model drug indomethacin (IMC via the solvent deposition method. Scanning electron microscopy (SEM, N2 adsorption, differential scanning calorimetry (DSC, and X-ray diffraction (XRD were applied to systematically characterize all IMC-loaded nanoporous silica formulations, evidencing the successful inclusion of IMC into nanopores, the reduced crystallinity, and finally accelerated dissolution of IMC. It was worth mentioning that, in comparison to 2D mesoporous silica, 3DOM silica displayed a more rapid release profile, which may be ascribed to the 3D interconnected pore networks and the highly accessible surface areas. The results obtained from the stability test indicated that the amorphous state of IMC entrapped in the 2D mesoporous silica (SBA-15 and MCM-41 has a better physical stability than in that of 3DOM silica. Moreover, the dissolution rate and stability of IMC loaded in 3DOM silica was closely related to the pore size of macroporous silica. The colorimetric 3-(4,5-Dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT and Cell Counting Kit (CCK-8 assays in combination with direct morphology observations demonstrated the good biocompatibility of nanoporous

  10. Synthesis of Alkyl-Glycerolipids Standards for Gas Chromatography Analysis: Application for Chimera and Shark Liver Oils

    Science.gov (United States)

    Pinault, Michelle; Guimaraes, Cyrille; Couthon, Hélène; Thibonnet, Jérôme; Fontaine, Delphine; Chantôme, Aurélie; Chevalier, Stephan; Jaffrès, Paul-Alain; Vandier, Christophe

    2018-01-01

    Natural O-alkyl-glycerolipids, also known as alkyl-ether-lipids (AEL), feature a long fatty alkyl chain linked to the glycerol unit by an ether bond. AEL are ubiquitously found in different tissues but, are abundant in shark liver oil, breast milk, red blood cells, blood plasma, and bone marrow. Only a few AEL are commercially available, while many others with saturated or mono-unsaturated alkyl chains of variable length are not available. These compounds are, however, necessary as standards for analytical methods. Here, we investigated different reported procedures and we adapted some of them to prepare a series of 1-O-alkyl-glycerols featuring mainly saturated alkyl chains of various lengths (14:0, 16:0, 17:0, 19:0, 20:0, 22:0) and two monounsaturated chains (16:1, 18:1). All of these standards were fully characterized by NMR and GC-MS. Finally, we used these standards to identify the AEL subtypes in shark and chimera liver oils. The distribution of the identified AEL were: 14:0 (20–24%), 16:0 (42–54%) and 18:1 (6–16%) and, to a lesser extent, (0.2–2%) for each of the following: 16:1, 17:0, 18:0, and 20:0. These standards open the possibilities to identify AEL subtypes in tumours and compare their composition to those of non-tumour tissues. PMID:29570630

  11. Measurement and modelization of silica opal optical properties

    OpenAIRE

    Avoine , Amaury; Ngoc Hong , Phan; Frederich , Hugo; Aregahegn , Kifle; Bénalloul , Paul; Coolen , Laurent; Schwob , Catherine; Thu Nga , Pham; Gallas , Bruno; Maître , Agnès

    2014-01-01

    International audience; We present the synthesis process and optical characterization of artificial silica opals. The specular reflection spectra are analyzed and compared to band structure calculations and finite difference time domain (FDTD) simulations. The silica optical index is a key parameter to correctly describe an opal and is usually not known and treated as a free parameter. Here we propose a method to infer the silica index, as well as the silica spheres diameter, from the reflect...

  12. The effect of alkylating agents on model supported metal clusters

    Energy Technology Data Exchange (ETDEWEB)

    Erdem-Senatalar, A.; Blackmond, D.G.; Wender, I. (Pittsburgh Univ., PA (USA). Dept. of Chemical and Petroleum Engineering); Oukaci, R. (CERHYD, Algiers (Algeria))

    1988-01-01

    Interactions between model supported metal clusters and alkylating agents were studied in an effort to understand a novel chemical trapping technique developed for identifying species adsorbed on catalyst surfaces. It was found that these interactions are more complex than had previously been suggested. Studies were completed using deuterium-labeled dimethyl sulfate (DMS), (CH{sub 3}){sub 2}SO{sub 4}, as a trapping agent to interact with the supported metal cluster ethylidyne tricobalt enneacarbonyl. Results showed that oxygenated products formed during the trapping reaction contained {minus}OCD{sub 3} groups from the DMS, indicating that the interaction was not a simple alkylation. 18 refs., 1 fig., 3 tabs.

  13. Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

    International Nuclear Information System (INIS)

    Alyoshina, Nonna A.; Parfenyuk, Elena V.

    2013-01-01

    A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N 2 adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica

  14. Novel Profluorescent Nitroxides for Monitoring Alkyl Radical Reactions During Radiation Degradation

    International Nuclear Information System (INIS)

    George, G.

    2006-01-01

    Hindered amine stabilizers (HAS) are effective at retarding the photo-oxidative and high energy radiation degradation of PP and in certain circumstances, also thermo-oxidative degradation. The effectiveness of HAS as retarders of oxidation relies on the oxidation of the N-C bond by polymer hydroperoxide, ROOH, to form the nitroxyl group -NO which is the scavenger of polymer alkyl radicals, R. This reaction, which produces the alkoxy amine: -NO-R, must be competitive with the reaction of R with oxygen (which gives the chain-carrying peroxy radical, RO 2 ) if this stabilization mechanism is to be important in the inhibition of radiation-induced oxidative degradation of polyolefins by HAS. The rate of this reaction is high and in solution the rate coefficient is from 1 to 9x10 8 l mol - 1 s - 1. The efficient radical trapping by nitroxides has been widely employed in spin-trapping studies by electron spin resonance (esr) spectroscopy]. In addition to the hindered piperidine structure of commercial HAS, more rigid aromatic systems have been studied that are more stable to oxidative degradation and are more efficient at scavenging alkyl radicals. One such family is the iso-indoline nitroxide system, TMDBIO, shown below which, as it contains the phenanthrene fluorophore, is termed phenanthrene nitroxide. This nitroxide only becomes fluorescent when it reacts with alkyl radicals or is reduced and is termed profluorescent. TMDBIO has a vanishingly small fluorescence quantum yield (φ∼10 - 4) due to the enhanced intersystem crossing from the first excited singlet state to the ground state due to electron exchange interactions of the nitroxyl radical. When the nitroxide traps an alkyl radical, R, the resulting alkoxy amine is fluorescent (φ∼10 - 1) and the emission intensity is a measure of the number of reactions that have occurred. This property may be exploited by using quantitative fluorescence spectroscopy to follow the reaction of the nitroxide with alkyl radicals

  15. Synthesis and Gas Transport Properties of Hyperbranched Polyimide–Silica Hybrid/Composite Membranes

    Directory of Open Access Journals (Sweden)

    Masako Miki

    2013-12-01

    Full Text Available Hyperbranched polyimide–silica hybrids (HBPI–silica HBDs and hyperbranched polyimide–silica composites (HBPI–silica CPTs were prepared, and their general and gas transport properties were investigated to clarify the effect of silica sources and preparation methods. HBPI–silica HBDs and HBPI–silica CPTs were synthesized by two-step polymerization of A2 + B3 monomer system via polyamic acid as precursor, followed by hybridizing or blending silica sources. Silica components were incorporated by the sol-gel reaction with tetramethoxysilane (TMOS or the addition of colloidal silica. In HBPI-silica HBDs, the aggregation of silica components is controlled because of the high affinity of HBPI and silica caused by the formation of covalent bonds between HBPI and silica. Consequently, HBPI-silica HBDs had good film formability, transparency, and mechanical properties compared with HBPI-silica CPTs. HBPI-silica HBD and CPT membranes prepared via the sol-gel reaction with TMOS showed specific gas permeabilities and permselectivities for CO2/CH4 separation, that is, both CO2 permeability and CO2/CH4 selectivity increased with increasing silica content. This result suggests that gas transport can occur through a molecular sieving effect of the porous silica network derived from the sol-gel reaction and/or through the narrow interfacial region between the silica networks and the organic matrix.

  16. Ruthenium-catalyzed direct C3 alkylation of indoles with α,β-unsaturated ketones.

    Science.gov (United States)

    Li, Shuai-Shuai; Lin, Hui; Zhang, Xiao-Mei; Dong, Lin

    2015-01-28

    In this paper, a simple and highly efficient ruthenium-catalyzed direct C3 alkylation of indoles with various α,β-unsaturated ketones without chelation assistance has been developed. This novel C-H activation methodology exhibits a broad substrate scope such as different substituted indoles, pyrroles, and other azoles. Further synthetic applications of the alkylation products can lead to more attractive 3,4-fused tricyclic indoles.

  17. Functionalized Mesoporous Silica Membranes for CO2 Separation Applications

    Directory of Open Access Journals (Sweden)

    Hyung-Ju Kim

    2015-01-01

    Full Text Available Mesoporous silica molecular sieves are emerging candidates for a number of potential applications involving adsorption and molecular transport due to their large surface areas, high pore volumes, and tunable pore sizes. Recently, several research groups have investigated the potential of functionalized mesoporous silica molecular sieves as advanced materials in separation devices, such as membranes. In particular, mesoporous silica with a two- or three-dimensional pore structure is one of the most promising types of molecular sieve materials for gas separation membranes. However, several important challenges must first be addressed regarding the successful fabrication of mesoporous silica membranes. First, a novel, high throughput process for the fabrication of continuous and defect-free mesoporous silica membranes is required. Second, functionalization of mesopores on membranes is desirable in order to impart selective properties. Finally, the separation characteristics and performance of functionalized mesoporous silica membranes must be further investigated. Herein, the synthesis, characterization, and applications of mesoporous silica membranes and functionalized mesoporous silica membranes are reviewed with a focus on CO2 separation.

  18. S - and N-alkylating agents diminish the fluorescence of fluorescent dye-stained DNA.

    Science.gov (United States)

    Giesche, Robert; John, Harald; Kehe, Kai; Schmidt, Annette; Popp, Tanja; Balzuweit, Frank; Thiermann, Horst; Gudermann, Thomas; Steinritz, Dirk

    2017-01-25

    Sulfur mustard (SM), a chemical warfare agent, causes DNA alkylation, which is believed to be the main cause of its toxicity. SM DNA adducts are commonly used to verify exposure to this vesicant. However, the required analytical state-of-the-art mass-spectrometry methods are complex, use delicate instruments, are not mobile, and require laboratory infrastructure that is most likely not available in conflict zones. Attempts have thus been made to develop rapid detection methods that can be used in the field. The analysis of SM DNA adducts (HETE-G) by immunodetection is a convenient and suitable method. For a diagnostic assessment, HETE-G levels must be determined in relation to the total DNA in the sample. Total DNA can be easily visualized by the use of fluorescent DNA dyes. This study examines whether SM and related compounds affect total DNA staining, an issue that has not been investigated before. After pure DNA was extracted from human keratinocytes (HaCaT cells), DNA was exposed to different S- and N-alkylating agents. Our experiments revealed a significant, dose-dependent decrease in the fluorescence signal of fluorescent dye-stained DNA after exposure to alkylating agents. After mass spectrometry and additional fluorescence measurements ruled out covalent modifications of ethidium bromide (EthBr) by SM, we assumed that DNA crosslinks caused DNA condensation and thereby impaired access of the fluorescent dyes to the DNA. DNA digestion by restriction enzymes restored fluorescence, a fact that strengthened our hypothesis. However, monofunctional agents, which are unable to crosslink DNA, also decreased the fluorescence signal. In subsequent experiments, we demonstrated that protons produced during DNA alkylation caused a pH decrease that was found responsible for the reduction in fluorescence. The use of an appropriate buffer system eliminated the adverse effect of alkylating agents on DNA staining with fluorescent dyes. An appropriate buffer system is thus

  19. Molecular Dynamics Simulations of Water Droplets On Hydrophilic Silica Surfaces

    DEFF Research Database (Denmark)

    Zambrano, Harvey A; Walther, Jens Honore; Jaffe, Richard L.

    2009-01-01

    and DNA microarrays technologies.Although extensive experimental, theoretical and computational work has been devoted to study the nature of the interaction between silica and water, at the molecular level a complete understanding of silica-water systems has not been reached. Contact angle computations...... dynamics (MD) simulations of a hydrophilic air-water-silica system using the MD package FASTTUBE. We employ quantum chemistry calculation to obtain air-silica interaction parameters for the simulations. Our simulations are based in the following force fields: i) The silica-silica interaction is based...... of water droplets on silica surfaces offers a useful fundamental and quantitative measurement in order to study chemical and physical properties of water-silica systems. For hydrophobic systems the static and dynamic properties of the fluid-solid interface are influenced by the presence of air. Hence...

  20. Silica scintillating materials prepared by sol-gel methods

    International Nuclear Information System (INIS)

    Werst, D.W.; Sauer, M.C. Jr.; Cromack, K.R.; Lin, Y.; Tartakovsky, E.A.; Trifunac, A.D.

    1993-01-01

    Silica was investigated as a rad-hard alternative to organic polymer hosts for organic scintillators. Silica sol-gels were prepared by hydrolysis of tetramethoxysilane in alcohol solutions. organic dyes were incorporated into the gels by dissolving in methanol at the sol stage of gel formation. The silica sol-gel matrix is very rad-hard. The radiation stability of silica scintillators prepared by this method is dye-limited. Transient radioluminescence was measured following excitation with 30 ps pulses of 20 MeV electrons

  1. Chemistry of the pyrazolidines. 26. Alkylation of 4-benzyliden-1-phenyl-3,5-dioxopyrazolidines

    International Nuclear Information System (INIS)

    Moldarev, B.L.; Aronzon, M.E.; Adanin, V.M.; Zyakun, A.M.

    1986-01-01

    The reaction of 4-benzyliden-1-phenyl-3,5-dioxopyrazolidines with alkyl halides in the presence of sodium alkoxide gave 1-phenyl-2-alkyl-4-benzyliden- and 1-phenyl-2,4-dialkyl-4-(α-alkoxybenzyl)-3,4-dioxopyrazolines. The structures of these compounds were confirmed by UV, IR, and PMR spectroscopy, and by mass-spectrometry

  2. Influence of organic solvents on interfacial water at surfaces of silica gel and partially silylated fumed silica

    Energy Technology Data Exchange (ETDEWEB)

    Turov, V.V.; Gun' ko, V.M.; Tsapko, M.D.; Bogatyrev, V.M.; Skubiszewska-Zieba, J.; Leboda, R.; Ryczkowski, J

    2004-05-15

    The effects of organic solvents (dimethylsulfoxide-d{sub 6} (DMSO-d{sub 6}), chloroform-d, acetone-d{sub 6}, and acetonitrile-d{sub 3}) on the properties of interfacial water at surfaces of silica gel Si-40 and partially silylated fumed silica A-380 were studied by means of the {sup 1}H NMR spectroscopy with freezing-out of adsorbed water at 180silicas and quantum chemical calculations of the chemical shifts {delta}{sub H} and solvent effects. DMSO-d{sub 6} and acetonitrile-d{sub 3} are poorly miscible with water in silica gel pores in contrast to the bulk liquids. DMSO-d{sub 6} and chloroform-d affect the structure of the interfacial water weaker than acetone-d{sub 6} and acetonitrile-d{sub 3} at amounts of liquids greater than the pore volume. Acetone-d{sub 6} and acetonitrile-d{sub 3} can displace water from pores under this condition. The chemical shift of protons in water adsorbed on silica gel is 3.5-6.5 ppm, which corresponds to the formation of two to four hydrogen bonds per molecule. Water adsorbed on partially silylated fumed silica has two {sup 1}H NMR signals at 5 and 1.1-1.7 ppm related to different structures (droplets and small clusters) of the interfacial water.

  3. Separation of products of alkylation of isobutane by olefins

    Energy Technology Data Exchange (ETDEWEB)

    Ward, J.

    1979-03-15

    The alkylation (A1) of isobutane (I) by propylene, butylene and amylenes is carried out at 24-52 degrees, pressure sufficient to maintain the liquid phase, and a molar ratio of I to olefins (O1) 10:1-15:1. The bulk ratio of catalysts to hydrocarbons in the reaction zone was 0.5:1-10:1; when using HF-K-T as the catalysts, it should contain less than 5 percent water and greater than or equal to 65 percent titrated HF. The hydrocarbon products (UP) from the alkylation zone are added after separating the catalyst in a fractionation tower; distillation is carried out at 38-49 degrees and 1.03-1.3 NPa. The head fraction containing I and less than 50 molar percent C3H8 and also fraction I at the point below the input side of the UP which contains less than 8 molar percent C3H8 and fraction n-C4H10 at the point below the point of discharge of fraction I is drained from the tower. The alkylate is discharged at the bottom of the tower. According to the patent the tower operates at low pressure. This improves relative volatility of individual components and reduces heat consumption. The best results are obtained when a head fraction or the concentration C3H8 approximately 25 molar percent is discharged.

  4. Thermodynamic calculation of simultaneous reactions of n-butane isomerization and isobutane alkylation with ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Batyrshin, N.N.; Beresneva, L.D.; Sidorov, V.A.

    1981-08-01

    Industrial production of ethylene alkylate has gained further development in connection with worldwide ecological problems and the planned changeover of automobile transport to unleaded gasolines, but the scale of production is still substantially less than that of sulfuric acid or hydrogen fluoride alkylates. This is due both to the instability of market prices for ethylene and the shortage of isobutane - a raw material for these large-tonnage production processes and for the synthetic rubber industry. The latter difficulty can be overcome by combining processes of isomerization of n-butane and alkylation of the resultant isobutane with ethylene in a single reaction unit. The possibility of combining these reactions using AlCl/sub 3/-based catalysts has been pointed out previously but in the literature there are no theoretical developments of technology or thermodynamic substantiation of a combined process. We have made a thermodynamic calculation of the consecutive (series-parallel) reactions of isomerization and alkylation with the goal of determining suitable technological conditions for carrying them out simultaneously and establishing the expected equilibrium yields of target products and the compositions of the reaction mixture.

  5. Hydride Transfer versus Deprotonation Kinetics in the Isobutane–Propene Alkylation Reaction: A Computational Study

    Science.gov (United States)

    2017-01-01

    The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C–C bond formation between a tert-butyl fragment and an additional olefin, or via deprotonation of the tert-butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle. PMID:29226012

  6. Hydride Transfer versus Deprotonation Kinetics in the Isobutane-Propene Alkylation Reaction: A Computational Study.

    Science.gov (United States)

    Liu, Chong; van Santen, Rutger A; Poursaeidesfahani, Ali; Vlugt, Thijs J H; Pidko, Evgeny A; Hensen, Emiel J M

    2017-12-01

    The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane-propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C-C bond formation between a tert -butyl fragment and an additional olefin, or via deprotonation of the tert -butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle.

  7. Photochemical generation and 1H NMR detection of alkyl allene oxides in solution

    International Nuclear Information System (INIS)

    Breen, L.E.; Schepp, N.P.; Tan, C.-H.E.

    2005-01-01

    Irradiation of substituted 5-alkyl-4,5-epoxyvalerophenones leads to the formation of alkyl allene oxides that, in some cases, are sufficiently long-lived to be detected at room temperature by 1 H NMR spectroscopy. Absolute lifetime measurements show that the size of the alkyl group has a significant influence on the reactivity of the allene oxide, with tert-butyl allene oxide having a lifetime of 24 h in CD 3 CN at room temperature that is considerably longer than the 1.5 h lifetime of the ethyl allene oxide. The allene oxides react rapidly with water to give α-hydroxyketones. The mechanism involves nucleophilic attack to the epoxide carbon to give an enol, which can also be detected as an intermediate by 1 H NMR spectroscopy. (author)

  8. A mild and efficient procedure for the synthesis of ethers from various alkyl halides

    Directory of Open Access Journals (Sweden)

    Mosstafa Kazemi

    2013-10-01

    Full Text Available A simple, mild and practical procedure has been developed for the synthesis of symmetrical and unsymmetrical ethers by using DMSO, TBAI in the presence of K2CO3. We extended the utility of Potassium carbonate as an efficient base for the preparation of ethers. A wide range of alkyl aryl and dialkyl ethers are synthezied from treatment of aliphatic alcohols and phenols with various alkyl halides in the prescence of efficient base Potassium carbonate. Secondary alkyl halides were easily converted to corresponding ethers in releatively good yields . This is a mild, simple and practical procedure for the preparation of ethers in high yields and suitable times under mild condition.

  9. Differential alkylation-based redox proteomics - Lessons learnt

    DEFF Research Database (Denmark)

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-01-01

    Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylati......Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S......-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here...... is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original...

  10. Effect of alkyl glycerophosphate on the activation of peroxisome proliferator-activated receptor gamma and glucose uptake in C2C12 cells

    Energy Technology Data Exchange (ETDEWEB)

    Tsukahara, Tamotsu, E-mail: ttamotsu@shinshu-u.ac.jp [Department of Integrative Physiology and Bio-System Control, Shinshu University School of Medicine, 3-1-1 Asahi, Matsumoto, Nagano 390-8621 (Japan); Haniu, Hisao [Department of Orthopedic Surgery, Shinshu University School of Medicine, 3-1-1 Asahi, Matsumoto, Nagano 390-8621 (Japan); Matsuda, Yoshikazu [Clinical Pharmacology Educational Center, Nihon Pharmaceutical University, Ina-machi, Saitama 362-0806 (Japan)

    2013-04-12

    Highlights: •Alkyl-LPA specifically interacts with PPARγ. •Alkyl-LPA treatments induces lipid accumulation in C2C12 cells. •Alkyl-LPA enhanced glucose uptake in C2C12 cells. •Alkyl-LPA-treated C2C12 cells express increased amounts of GLUT4 mRNA. •Alkyl-LPA is a novel therapeutic agent that can be used for the treatment of obesity and diabetes. -- Abstract: Studies on the effects of lipids on skeletal muscle cells rarely examine the effects of lysophospholipids. Through our recent studies, we identified select forms of phospholipids, such as alkyl-LPA, as ligands for the intracellular receptor peroxisome proliferator-activated receptor gamma (PPARγ). PPARγ is a nuclear hormone receptor implicated in many human diseases, including diabetes and obesity. We previously showed that alkyl-LPA is a specific agonist of PPARγ. However, the mechanism by which the alkyl-LPA–PPARγ axis affects skeletal muscle cells is poorly defined. Our objective in the present study was to determine whether alkyl-LPA and PPARγ activation promotes glucose uptake in skeletal muscle cells. Our findings indicate that PPARγ1 mRNA is more abundant than PPARγ2 mRNA in C2C12 cells. We showed that alkyl-LPA (3 μM) significantly activated PPARγ and increased intracellular glucose levels in skeletal muscle cells. We also showed that incubation of C2C12 cells with alkyl-LPA led to lipid accumulation in the cells. These findings suggest that alkyl-LPA activates PPARγ and stimulates glucose uptake in the absence of insulin in C2C12 cells. This may contribute to the plasma glucose-lowering effect in the treatment of insulin resistance.

  11. Effect of alkyl glycerophosphate on the activation of peroxisome proliferator-activated receptor gamma and glucose uptake in C2C12 cells

    International Nuclear Information System (INIS)

    Tsukahara, Tamotsu; Haniu, Hisao; Matsuda, Yoshikazu

    2013-01-01

    Highlights: •Alkyl-LPA specifically interacts with PPARγ. •Alkyl-LPA treatments induces lipid accumulation in C2C12 cells. •Alkyl-LPA enhanced glucose uptake in C2C12 cells. •Alkyl-LPA-treated C2C12 cells express increased amounts of GLUT4 mRNA. •Alkyl-LPA is a novel therapeutic agent that can be used for the treatment of obesity and diabetes. -- Abstract: Studies on the effects of lipids on skeletal muscle cells rarely examine the effects of lysophospholipids. Through our recent studies, we identified select forms of phospholipids, such as alkyl-LPA, as ligands for the intracellular receptor peroxisome proliferator-activated receptor gamma (PPARγ). PPARγ is a nuclear hormone receptor implicated in many human diseases, including diabetes and obesity. We previously showed that alkyl-LPA is a specific agonist of PPARγ. However, the mechanism by which the alkyl-LPA–PPARγ axis affects skeletal muscle cells is poorly defined. Our objective in the present study was to determine whether alkyl-LPA and PPARγ activation promotes glucose uptake in skeletal muscle cells. Our findings indicate that PPARγ1 mRNA is more abundant than PPARγ2 mRNA in C2C12 cells. We showed that alkyl-LPA (3 μM) significantly activated PPARγ and increased intracellular glucose levels in skeletal muscle cells. We also showed that incubation of C2C12 cells with alkyl-LPA led to lipid accumulation in the cells. These findings suggest that alkyl-LPA activates PPARγ and stimulates glucose uptake in the absence of insulin in C2C12 cells. This may contribute to the plasma glucose-lowering effect in the treatment of insulin resistance

  12. Surface characterization of polyethylene terephthalate/silica nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Parvinzadeh, Mazeyar, E-mail: mparvinzadeh@gmail.com [Department of Textile, Islamic Azad University, Science and Research Branch, Tehran (Iran, Islamic Republic of); Moradian, Siamak [Department of Polymer and Color Engineering, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran (Iran, Islamic Republic of); Rashidi, Abosaeed [Department of Textile, Islamic Azad University, Science and Research Branch, Tehran (Iran, Islamic Republic of); Yazdanshenas, Mohamad-Esmail [Department of Textile, Islamic Azad University, Yazd Branch, Yazd (Iran, Islamic Republic of)

    2010-02-15

    Poly(ethylene terephthalate) (PET) based nanocomposites containing hydrophilic (i.e. Aerosil 200 or Aerosil TT 600) or hydrophobic (i.e. Aerosil R 972) nano-silica were prepared by melt compounding. Influence of nano-silica type on surface properties of the resultant nanocomposites was investigated by the use of Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), contact angle measurement (CAM), scanning electron microscopy (SEM) and reflectance spectroscopy (RS). The possible interaction between nano-silica particles and PET functional groups at bulk and surface were elucidated by transmission FTIR and FTIR-ATR spectroscopy, respectively. AFM studies of the resultant nanocomposites showed increased surface roughness compared to pure PET. Contact angle measurements of the resultant PET composites demonstrated that the wettability of such composites depends on surface treatment of the particular nano-silica particles used. SEM images illustrated that hydrophilic nano-silica particles tended to migrate to the surface of the PET matrix.

  13. New insight into silica deposition in horsetail (Equisetum arvense

    Directory of Open Access Journals (Sweden)

    Exley Christopher

    2011-07-01

    Full Text Available Abstract Background The horsetails (Equisetum sp are known biosilicifiers though the mechanism underlying silica deposition in these plants remains largely unknown. Tissue extracts from horsetails grown hydroponically and also collected from the wild were acid-digested in a microwave oven and their silica 'skeletons' visualised using the fluor, PDMPO, and fluorescence microscopy. Results Silica deposits were observed in all plant regions from the rhizome through to the stem, leaf and spores. Numerous structures were silicified including cell walls, cell plates, plasmodesmata, and guard cells and stomata at varying stages of differentiation. All of the major sites of silica deposition in horsetail mimicked sites and structures where the hemicellulose, callose is known to be found and these serendipitous observations of the coincidence of silica and callose raised the possibility that callose might be templating silica deposition in horsetail. Hydroponic culture of horsetail in the absence of silicic acid resulted in normal healthy plants which, following acid digestion, showed no deposition of silica anywhere in their tissues. To test the hypothesis that callose might be templating silica deposition in horsetail commercially available callose was mixed with undersaturated and saturated solutions of silicic acid and the formation of silica was demonstrated by fluorimetry and fluorescence microscopy. Conclusions The initiation of silica formation by callose is the first example whereby any biomolecule has been shown to induce, as compared to catalyse, the formation of silica in an undersaturated solution of silicic acid. This novel discovery allowed us to speculate that callose and its associated biochemical machinery could be a missing link in our understanding of biosilicification.

  14. Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

    Energy Technology Data Exchange (ETDEWEB)

    Alyoshina, Nonna A.; Parfenyuk, Elena V., E-mail: evp@iscras.ru

    2013-09-15

    A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N{sub 2} adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica.

  15. Alkyl chain length impacts the antioxidative effect of lipophilized ferulic acid in fish oil enriched milk

    DEFF Research Database (Denmark)

    Sørensen, Ann-Dorit Moltke; Lyneborg, Karina Sieron; Villeneuve, Pierre

    2015-01-01

    Lipophilization of phenolics by esterification with fatty alcohols may alter their localization in an emulsion and thereby their antioxidant efficacy. In this study, synthesized unbranched alkyl ferulates were evaluated as antioxidants in fish oil enriched milk. Lipid oxidation was determined...... by peroxide values and concentration of volatile oxidation products. A cut-off effect in the antioxidant efficacy in relation to the alkyl chain length was observed. The most efficient alkyl ferulate was methyl ferulate followed by ferulic acid and butyl ferulate, whereas octyl ferulate was prooxidative...

  16. Some features of formation and dissolution of a series of Pu(IV) and Zr alkyl and butyl alkyl phosphates in the system TBP -n-dodecane - nitric acid - water

    International Nuclear Information System (INIS)

    Markov, G.S.; Moshkov, M.M.; Kokina, S.A.

    1990-01-01

    The formation and composition of salts produced on interaction of a series of alkyl- and butylalkylphosphoric acids having alkyl radical chain lengths from C 4 to C 1 0 with Pu(IV) and Zr in organic and aqueous phases of the system TBP - n-dodecane -nitric acid - water were studied. The composition of compounds was found to depend on the conditions of their formation, defined first of all by the HNO 3 concentration in aqueous and organic phases. (author) 12 refs.; 4 figs.; 1 tab

  17. Microtubule disruption induced in vivo by alkylation of beta-tubulin by 1-aryl-3-(2-chloroethyl)ureas, a novel class of soft alkylating agents.

    Science.gov (United States)

    Legault, J; Gaulin, J F; Mounetou, E; Bolduc, S; Lacroix, J; Poyet, P; Gaudreault, R C

    2000-02-15

    We have previously reported that 4-tert-butyl-[3-(2-chloroethyl)ureido] benzene (4-tBCEU), a potent cytotoxic agent, modulates the synthesis of tubulins, suggesting that its cytotoxicity may be mediated through an antimicrotubule mechanism. Indeed, 4-tBCEU and its 4-iso-propyl (4-isopropyl [3-(2-chloroethyl)ureido] benzene) and 4-sec-butyl (4-sec-butyl [3-(2-chloroethyl)ureido] benzene) homologues induced disruption of the cytoskeleton and arrest of the cell cycle in G2 transition and mitosis. To better understand the mechanisms responsible for microtubule disruption by 1-aryl-3-(2-chloroethyl)ureas (CEU), we first examined their cytotoxicity on Chinese hamster ovary cells resistant to vinblastine and colchicine due to the expression of mutated tubulins (CHO-VV 3-2). These cells showed resistance to CEU, e.g., 4-tBCEU having an IC50 of 21.3+/-1.1 microM as compared with an IC50 of 11.6+/-0.7 microM for wild-type cells, suggesting a direct effect of the drugs on tubulins. Western blot analysis confirmed the disruption of microtubules and evidenced the formation of an additional immunoreactive beta-tubulin with an apparent lower molecular weight on SDS polyacrylamide gel. Incubation of MDA-MB-231 cells with [urea-14C]-4-tBCEU revealed the presence of a radioactive protein that coincided with the additional beta-tubulin band, indicating that CEU could covalently bind to the beta-tubulin. The 4-tBCEU-binding site on beta-tubulin was identified by competition of the CEU with colchicine, vinblastine, and iodoacetamide, a specific alkylating agent of sulfhydryl groups of cysteine residues. Colchicine, but not vinblastine, prevented the formation of the additional beta-tubulin band, suggesting that 4-tBCEU alkylates either Cys239 or Cys354 residues near the colchicine-binding site. To determine the cysteine residue alkylated by 4-tBCEU, we incubated the radiolabeled drug with human neuroblastoma cells (SK-N-SH) that overexpress the betaIII-tubulin, an isoform where Cys239

  18. Industrial tests of a new technology for sulfuric acid alkylation of isobutane by olefines

    Energy Technology Data Exchange (ETDEWEB)

    Tarakanov, V.S.; Karamyshev, M.S.; Khadzhiyev, S.N.; Mel' man, A.Z.

    1971-01-01

    A complex of elements of a new technology for sulfuric acid alkylation of isobutane by alkenes with the use of a KSG-2 reactor and an acetic settler of a new design is realized as a result of the joint work of the Novo-Yaroslav oil refinery, GrozNII, VNIIOINeft and VNIINeftemash in an alkylation installation.

  19. Reinforcement of natural rubber hybrid composites based on marble sludge/Silica and marble sludge/rice husk derived silica

    Directory of Open Access Journals (Sweden)

    Khalil Ahmed

    2014-03-01

    Full Text Available A research has been carried out to develop natural rubber (NR hybrid composites reinforced with marble sludge (MS/Silica and MS/rice husk derived silica (RHS. The primary aim of this development is to scrutinize the cure characteristics, mechanical and swelling properties of such hybrid composite. The use of both industrial and agricultural waste such as marble sludge and rice husk derived silica has the primary advantage of being eco-friendly, low cost and easily available as compared to other expensive fillers. The results from this study showed that the performance of NR hybrid composites with MS/Silica and MS/RHS as fillers is extremely better in mechanical and swelling properties as compared with the case where MS used as single filler. The study suggests that the use of recently developed silica and marble sludge as industrial and agricultural waste is accomplished to provide a probable cost effective, industrially prospective, and attractive replacement to the in general purpose used fillers like china clay, calcium carbonate, and talc.

  20. Study of hydrogen mobility by hydrogen-deuterium exchange. II. Theoretical kinetic study in alkyl and amino-alkyl pyrimidines

    International Nuclear Information System (INIS)

    Pompon, Alain

    1975-01-01

    Alkyl groups bound to the pyrimidine ring can be deuterium substituted on the carbon adjacent to the ring, in acidic D 2 O; kinetic equations corresponding to various exchange mechanism hypothesis are established. It is shown that theoretical and experimental results can be compared in order to precise the mechanism and to measure the characteristic parameters of the exchange reaction [fr