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  • Physical Chemistry  (6)
  • sulfone  (4)
  • central nervous system  (3)
  • Wiley-Blackwell  (13)
  • 1
    Electronic Resource
    Electronic Resource
    Synthesis and properties of poly(oxyethylene)s containing thioether, sulfoxide, or sulfone groups (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 793-801 
    Details
    ISSN: 0887-624X
    Keywords: poly(oxyethylene) ; thioether ; sulfoxide ; sulfone ; copolymer ; solubility ; glass transition temperature ; substitution ; oxidation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly[oxy(ethylthiomethyl)ethylene] (ETE) was prepared from poly[oxy (chloromethyl)ethylene] (CE) by reaction with sodium ethanethiolate. Sulfoxide and sulfone analogues were synthesized by oxidation of the poly[oxy(ethylthiomethyl)ethylene]. By changing the chloromethyl/sodium ethanethiolate ratio, poly[oxy (chloromethyl)ethylene-co-oxy(ethylthiomethyl)ethylene] (CE-ETEs) were easily made. Poly[oxy(ethylsulfinylmethyl)ethylene] (ESXE), poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfinylmethyl)ethylene] (CE-ESXEs), poly[oxy(ethylsulfonylmethyl)ethylene] (ESE), and poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfonylmethyl)ethylene] (CE-ESEs) were obtained by oxidation of ETE or CE-ETEs. There was little if any chain degradation. The (co)polymer structures were confirmed by FTIR and 1H-NMR spectroscopic studies. Their thermal properties were studied by DSC and TGA. Tgs of ETE, ESXE, and ESE were -57, 36, and 57°C, respectively, and Td,os (initial decomposition temperature, TGA) were 331, 198, and 308°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 793-801, 1998
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Oxyethylene copolymers with chloromethyl and (alkylthio)methyl or (alkylsulfonyl)methyl side groups: Syntheses and Tg/composition relationships (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 495-504 
    Details
    ISSN: 0887-624X
    Keywords: copolymer ; glass transition temperature ; Fox equation ; sulfone ; thioether ; oxyethylene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New classes of copolymers, poly[oxy(chloromethyl)ethylene]/poly[oxy-((alkylthio)methyl)ethylene] copolymers (CE-ATEs), poly[oxy((alkylthio)methyl)-ethylene]s (ATEs), poly[oxy(chloromethyl)ethylene]/poly[oxy((alkylsulfonyl)meth-yl)ethylene] copolymers (CE-ASEs), and poly[oxy((alkylsulfonyl)methyl)ethylene]s (ASEs) have been made for the first time. The thioether-containing polymers (CE-ATEs and ATEs) were synthesized by reacting poly[oxy(chloromethyl)ethylene] (CE, poly(epichlorohydrin)) with different amounts of sodium alkanethiolates. The sulfone-containing polymers (CE-ASEs and ASEs) were synthesized by oxidizing the CE-ATEs and ATEs using m-chloroperoxybenzoic acid. The Fox equation, a linear relationship, fit the Tg/composition data for most CE-ATEs. The Tg's of the CE-ASEs showed positive deviations from those calculated using the Fox equation. The Johnston equation, in which steric and/or polar interactions between dissimilar monomeric units are considered by using TgAB (the Tg of the AB or BA dyad), fit the Tg/composition data for all copolymers in this study. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 495-504, 1998
    Additional Material: 6 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Synthesis and characterization of poly(ethylene oxide-co-ethylene sulfone)s and their precursors: Poly(ethylene oxide-co-ethylene sulfide)s (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1323-1330 
    Details
    ISSN: 0887-624X
    Keywords: sulfide ; ethylene ; sulfone ; oxide ; 1,2-ethane dithiol synthesis ; oxidation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three poly(ethylene oxide-co-ethylene sulfide)s with oxygen to sulfur ratios of 2/1, 2/2, and 1/2 were prepared by phase-transfer catalyzed polycondensations of (1) sodium sulfide and 1,2-bis (2-chloroethoxy)ethane, (2) 1,2-ethanedithiol and 1,2-bis(2-chloroethoxy)ethane, and (3) 1,2-ethanedithiol and 2-chloroethyl ether, respectively. A buffered solution with pH between the pKa of the monothiol (RSH) and the pKa2 of the dithiol (HS-R-SH), or H2S, was needed to obtain high molecular weight polymers, which suggests that nucleophiles transfer and react as monoanions rather than dianions. These poly(ethylene oxide-co-ethylene sulfide)s were oxidized completely to poly(ethylene oxide-co-ethylene sulfone)s using 3-chloroperoxybenzoic acid as oxidant. Both the final polymers and the precursors have regular sequenced structures and are semicrystalline. As expected, their glass transition temperatures and melting points increase and solubilities decrease with the decrease of ether oxygen to sulfur ratio. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1994.080320713
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  • 4
    Electronic Resource
    Electronic Resource
    Oxyalkylene polymers with alkylsulfonylmethyl side chains: Gas barrier properties (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 75-83 
    Details
    ISSN: 0887-6266
    Keywords: barrier polymer ; permeability coefficient ; glass transition temperature ; blend ; sulfone ; oxyethylene ; oxytrimethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas barrier properties of alkylsulfonylmethyl-substituted poly(oxyalkylene)s are discussed. Oxygen permeability coefficients of three methylsulfonylmethyl-substituted poly(oxyalkylene)s, poly[oxy(methylsulfonylmethyl)ethylene] (MSE), poly[oxy(methylsulfonylmethyl)ethylene-co-oxyethylene] (MSEE), and poly[oxy-2,2-bis (methylsulfonylmethyl)trimethylene oxide] (MST) were measured. MSEE, which has the most flexible backbone of the three polymers, had an oxygen permeability coefficient at 30°C of 0.0036 × 10-13 cm3(STP)·cm/cm2·s·Pa higher than that of MSE, 0.0014 × 10-13 cm3(STP)·cm/cm2·s·Pa, because the former polymer's Tg was near room temperature. MST with two polar groups per repeat unit and the highest Tg showed the highest oxygen permeability, 0.013 × 10-13 cm3(STP) · cm/cm2·s·Pa, among the three polymers, probably because steric hindrance between the side chains made the chain packing inefficient. As the side chain length of poly[oxy(alkylsulfonylmethyl)ethylene] increased, Tg and density decreased and the oxygen permeability coefficients increased. The oxygen permeability coefficient of MSE at high humidity (84% relative humidity) was seven times higher than when it was dry because absorbed water lowered its Tg. At 100% relative humidity MSE equilibrated to a Tg of 15°C after 2 weeks. A 50/50 blend of MSE/MST had oxygen barrier properties better than the individual polymers (O2 permeability coefficient is 0.0007 × 10-13 cm3(STP)·cm/cm2 ·s·Pa), lower than most commercial high barrier polymers. At 100% relative humidity, it equilibrated to a Tg of 42°C, well above room temperature. These are polymer systems with high gas barrier properties under both dry and wet conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 75-83, 1998
    Additional Material: 5 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Interrelations Of the energetics of amides and alkenes: Enthalpies of formation of N,N-dimethyl derivatives of pivalamide, 1-adamantylcarboxamide and benzamide, and of styrene and its α-, trans-β- and β,β-methylated derivatives (1995)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 15-25 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The enthalpies of formation of the condensed phase and gaseous N,N-dimethyl derivatives of pivalamide, 1-adamantylcarboxamide and benzamide were determined by combustion calorimetry and the associated enthalpies of vaporization and sublimation. The enthalpies of formation of styrene and its α-, trans-β- and β,β-methylated derivatives were determined from measurements of their enthalpies of hydrogenation in dilute hydrocarbon solution. Strain and resonance effects of amides and alkenes are discussed in terms of the exo-/endothermicity of the following reactions: and in terms of the difference of enthalpies of formation of the isomeric (Z)- and E-RCH=CHCH3.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610080105
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  • 6
    Electronic Resource
    Electronic Resource
    Effects of concurrent exposure to 60 Hz electric and magnetic fields on the social behavior of baboons (1995)
    New York, NY [u.a.] : Wiley-Blackwell
    Bioelectromagnetics 16 (1995), S. 71-92 
    Details
    ISSN: 0197-8462
    Keywords: Papio cynocephalus anubis ; biological effects ; central nervous system ; nonhuman primates ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Our previous research has demonstrated that 30 or 60 kV/m electric fields (EF) reliably produce temporary increases in the performance of three categories of baboon social behavior: Passive Affinity, Tension, and Stereotypy. The experimental design included 6 week preexposure, exposure, and postexposure periods with experimental and control groups, each with eight subjects. Here, we report two experiments that evaluated the effects of combined EF and magnetic fields (MF) on baboon social behavior. One experiment demonstrated that exposure to 6 kV/m EF and 50 μT (0.5 G) MF produced Period × Group interactions for Stereotypy and Attack, but the previously observed increases in Passive Affinity, Tension, and Stereotypy did not occur. A second experiment demonstrated that exposure to 30 kV/m EF and 100 μT 1.0 G MF did not produce the same magnitude of increases in Passive Affinity, Tension, and Stereotypy observed previously with 30 kV/m EF alone. The exposed group exhibited decreased performance rates for several behavior categories during exposure with further declines during postexposure. The control group showed fewer downward trends across periods. © 1995 Wiley-Liss, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bem.2250160708
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  • 7
    Electronic Resource
    Electronic Resource
    Effects of exposure to a 60-kV/m, 60-Hz electric field on the social behavior of baboons (1991)
    New York, NY [u.a.] : Wiley-Blackwell
    Bioelectromagnetics 12 (1991), S. 361-375 
    Details
    ISSN: 0197-8462
    Keywords: electric-field effects ; stress ; central nervous system ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: We found in a previously reported study that exposure to a 30-kV/m, 60-Hz electric field had significant effects on the social behavior of baboons. However, it was not established whether or not the effects were related specifically to the 30-kV/m intensity of the field. A new experiment was conducted to determine whether or not exposure to a 60-Hz electric field at 60 kV/m would produce like changes in the baboons' social behavior. We exposed one group of eight male baboons to an electric field 12 hours a day, 7 days a week, for 6 weeks. A second group of eight animals was maintained under sham-exposure (control) conditions. Rates of performing on each of six categories of social behavior and on four categories of nonsocial behavior were used as criteria for comparing exposed with unexposed subjects and for within-group comparisons during three six-week experimental periods: Pre-Exposure, Exposure, and Post-Exposure. The results indicate that (1) during the exposure period, exposed animals exhibited statistically significant differences from controls in means of performance rates based on several behavioral categories; (2) across all three periods, within-group comparisons revealed that behaviors of exposed baboons were significantly affected by exposure to the electric field; (3) changes in performance levels probably reflect a stress response to the electric field; and (4) the means of response rates of animals exposed at 60 kV/m were higher, but not double, those of animals exposed at 30 kV/m. As in the 30-kV/m experiment, animals exposed at 60 kV/m exhibited significant differences in performances of Passive Affinity, Tension, and Stereotypy. Mean rates of performing these categories were 122% (Passive Affinity), 48% (Tension), and 40% (Stereotypy) higher in the exposed group than in the control group during exposure to the 60-kV/m field.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bem.2250120605
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  • 8
    Electronic Resource
    Electronic Resource
    Effects of exposure to 30 kV/m, 60-Hz electric fields on the social behavior of baboons (1991)
    New York, NY [u.a.] : Wiley-Blackwell
    Bioelectromagnetics 12 (1991), S. 117-135 
    Details
    ISSN: 0197-8462
    Keywords: Biological effects ; social behavior ; stress ; central nervous system ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: We tested the hypothesis that exposure to a 30-kY/m, 60-Hz electric field produces significant change (stress) in the social behavior of adult male baboons (Papio cynocephalus anubis). One group of eight baboons was exposed to an electric field (12 hours per day, 7 days per week for 6 weeks) while a second group of eight baboons was maintained in a sham-exposure (control) condition. Exposed subjects and control subjects were compared over three, six-week experimental periods (pre-exposure, exposure, and post-exposure). Performance rates of six categories of social behaviors (passive affinity, active affinity, approach, tension, threat, and attack) and four categories of nonsocial behaviors (forage, manipulate, posture, and stereotypy) were used to compare the two groups. The results of our study indicate that 1) there were no significant differences between the two groups during the pre-exposure or post-exposure periods; 2) during the exposure period, experimental and control groups exhibited statistically significant differences in the mean performance rates of three behavior categories; 3) within-group comparisons across periods indicate that the experimentally exposed group exhibited statistically significant changes in passive affinity, tension, and stereotypy; and 4) changes in behavior performance among the exposed subjects reflect a stress response to the electric field.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bem.2250120206
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  • 9
    Electronic Resource
    Electronic Resource
    Consistency of theory and experiment in the ethane-methyl radical system (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 481-495 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of ethane has been reinvestigated using the single pulse, reflected shock technique. Reflected shock temperatures were corrected for boundary layer-induced nonidealities using the thermal decomposition of cyclohexene as a kinetic standard. The rate constant for the reaction was calculated from the rate of formation of methane under conditions of very low extent of reaction, over a temperature range of 1000-1241 K. Ethane compositions of 1% and 3% in argon at total reaction pressures of 3 and 9 atm were used, and a small pressure dependence of k1 was observed.An RRKM model is described which gives excellent agreement with this and other recent dissociation and recombination rate constant data in light of a recent revision to the thermochemistry of the methyl radical. In the range of 1000-1300 K an RRKM extrapolated k1∞ is given by the expression, log k1∞ = 17.2 - 91,000/2.3RT, while at 298 K the calculation gives log k-1∞ (l/mol sec) = 10.44, where k-1∞ is calculated from k1∞ and the equilibrium constant.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130506
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  • 10
    Electronic Resource
    Electronic Resource
    Mechanism of the silane decomposition. I. Silane loss kinetics and rate inhibition by hydrogen. II. Modeling of the silane decomposition (all stages of reaction) (1985)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 1029-1065 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Part I: Kinetic data for the static system silane pyrolysis (from 640-703 K, 60-400 torr) are presented. For conversion from 3-30%, first-order kinetics are obtained, with silane loss rates equal to half the hydrogen formation rates. At conversions greater than 40%, rate inhibition attributable to the back reaction of hydrogen with silylene occurs. Overall reaction rates are not surface sensitive, but disilane and trisilane yield maxima under some conditions are. A nonchain mechanism capable of describing quantitatively all stages of the silane pyrolysis is proposed. Post 1.0% initiation is both homogeneous (gas phase) and heterogeneous (on the walls), and reaction intermediates are silylenes and disilenes. Free radicals are not involved at any stage of the reaction. Rate data at high conversions and with added hydrogen provide kinetics for the addition of silylene to hydrogen [reaction (-1)1] relative to its addition to silane [reaction (2)]: k-1,/k2 = 10-0.65 × e-3200 cal/RT. With E2 = 1300 cal, this gives a high pressure activation energy for silylene insertion into hydrogen of E-1 = 8200 cal.Part II: An analysis is made of each rate constant of the silane mechanism and the modeling results are compared with experimental results. Agreement is excellent. It is concluded that the dominant sink reaction for silylene intermediates is 1,2 - H2 elimination from disilane (followed by Si2H4 polymerization and wall deposition). The model is in accord with slow isomerization between disilene and silylsilylene and near exclusive 1,2 - H2 elimination from Si2H6. It is also concluded that disilene is about 10 kcal/mol more stable than silylsilylene and that the activation energy for isomerization of silylsilylene to disilene is greater than 26 kcal/mol.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550171003
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