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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein auf Magnesiumoxid aufgebrachter Polytitazan-Cobalt (III)-Komplex diente als effektiver Katalysator für die Epoxidierung von cis-Cycloocten mit molekularem Sauerstoff bei Normaldruck in Gegenwart von Isobutyraldehyd als Reduktionsmittel. Nach XPS-Untersuchungen wird Cobalt (III) durch den mehrzähnigen Stickstoffliganden des Polytitazans stabilisiert. Bei 25°C beträgt der cis-Cycloocten-Umsatz nach fünf Stunden 95,2%, mit einer Selektivität von 100% für das cis-Cyclohexylenoxid. Der Katalysator Kann mindestens neun Mal ohne Aktivitätsverlust verwendet werden.
    Notes: Magnesium oxide supported polytitazane cobalt (III) complex is demonstrated as an effective catalyst for the epoxidation of cis-cyclooctene with molecular oxygen at atmospheric pressure in the presence of isobutyraldehyde as the sacrificial reductant. XPS data show that the high-valent cobalt (III) is stabilized by the multidentate nitrogen ligand of polytitazane. The conversion of cis-cyclooctene is as high as 95.2% with 100% selectivity to the cis-cyclooctene oxide at 25°C within 5 h. The catalyst can be used at least nine times without loss of its activity.
    Additional Material: 2 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 243 (1996), S. 177-187 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird über die Gleichgewichts-Schmelzpunktsdepression von Polycarbonat aus Bisphenol A (PC) in Mischungen mit Poly-∊-caprolacton (PCL) berichtet. Hierzu wird ein Modell entwickelt, das den gekrümmten Verlauf der gemessenen Hoffman-Weeks-Plots zu erklären vermag. Es berücksichtigt die Konzentrationsinhomogenitäten, die mit fortschreitender Kristallisation an der Kristallwachstumsfront entstehen. Die gelegentlich beobachtete Schmelzpunktsdepression der PCL-Komponente wird diskutiert. Der Flory-Hugginssche Wechselwirkungsparameter wird zu -0,09 berechnet; aus diesem kleinen Wert muß geschlossen werden, daß die Mischungspartner enthalpisch nur schwach wechselwirken. Der merkliche Abfall der Glastemperatur des PC nach Einmischen von PCL bewirkt eine beträchtliche Kristallisation aus der Schmelze; es können PC-Kristallinitätsgrade bis zu 25% erreicht werden.
    Notes: It is reported on the equilibrium melting point depression of polycarbonate from bisphenol A (PC) in its blend with poly-∊-caprolactone (PCL). To this end, a model which explains the bended course of the measured Hoffman-Weeks plots is developed which takes into account the composition changes at the crystal growth front upon progressive crystallization. The occasional melting point depression of the PCL component is discussed. The calculated Flory-Huggins parameter of χ12 ≍ -0.09 indicates only weak enthalpic interactions. The remarkable drop in the glass transition temperature of PC with blending allows PC degrees of crystallinity up to 25% upon crystallization from the melt.
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  • 3
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Attachment of the side-chain carboxyl of the protected aspartic or glutamic acid ester to the resin support has been established for the solid-phase synthesis of the asparagine or glutamine peptide. After further elongation of the α-amino deprotected resin-bound peptide ester with protected peptide fragments and the final detachment from the resin support by ammonolysis, the larger peptides containing, or preferably C-terminated with, asparagine or glutamine could be obtained. Thus, the C-peptide of human proinsulin was prepared by coupling to the resin-bound dipeptide derivative, Leu-Glu(OCH2Ph®)·OtBu, with six fragments consecutively. It was obtained in an overall yield of 36% after detaching from the resin with alcoholic ammonia, followed by mild acidolysis, DEAE cellulose chromatography, and gel filtration. This procedure has now been applied to the synthesis of the C-terminal fragment of the insulin A chain ending in asparagine, and also to the synthesis of the threonine or serine peptide, where the anchorage to the resin was designed by the reaction of the sidechain hydroxyl with succinic anhydride in the presence of 4-dimethylaminopyridine to form the hemiester of succinic acid, which in turn was condensed to the aminomethyl resin by the DCC-HOBt procedure. Model experiments on the synthesis of the Z-Thr(CO-CH2CH2CONHCH2Ph®)·OtBu and Bpoc-Lys(Boc)-Thr(COCH2CH2CONHCH2Ph®)·OtBu, as well as their detachment from the resin by amminolysis or hydrazinolysis, have shown the potential for a milder process in the solid-phase synthesis of larger peptides.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 41 (1997), S. 121-130 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has very recently been reported that deoxyribonucleic acid oligomers of cytosine with sequences such as d-T(CN)T aggregate into tetrastranded sructures [J. L. Leroy et al. (1993), Biochemistry, Vol. 32, pp. 6019-6031; K. Gehring et al. (1993), Nature, Vol. 363, pp. 561-565; S. Ahmed (1994), Structural Biology, Vol. 1, pp. 83-88]. Using gel filtration chromatography we have found that the oligomer dC10 aggregates into a mixture of duplex, tetraplex, and octaplex structures. We have also found that at the concentration used for Raman spectroscopy (0.05 M in base residues), these structures remain stable from pH 5 to pH 8 at 5°C. The Raman spectra of these oligomers in a 0.1 M NaCl solution at pH 7 and 5°C show a remarkable resemblance to the Raman spectra of the A-form double-helical ribonucleic acid polymer of cytosine taken at pH 5.5 and room temperature [C. H. Chen and G. J. Thomas, Jr. (1977), Biopolymers, Vol. 16, pp. 765-789]. This appears to be the first time that this A-type furanose ring pucker has been reported in deoxyoligonucleotides in aqueous solution at low salt and pH 5.5-7. The gel filtration chromatography and the uv melting behavior of the annealed dC10 solutions show the presence of an equilibrium mixture of multiplexes with multiple melting transitions. Very slow annealing of dC10 solutions in the pH range 6.5-7.0 also produced a similar equilibrium mixture of multiplexes, but at a much slower rate. Rapidly cooled samples tended to change to the equilibrium mixture over a period of several days. © 1997 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
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  • 5
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel and more efficient synthesis of 14-alkoxy-substituted indolo- and benzofuro-morphinans in three steps starting from either naltrindole (1) or naltriben (2), using methoxymethyl or silyl protecting groups, is reported. The 14-O-alkyl group is introduced at the penultimate step of the procedure. This is an additional advantage of the described procedure since the late introduction of the 14-O-alkyl group makes it much easier to produce a greater diversity of 14-alkoxy derivatives in this series of δ opioid receptor antagonists. Thus, compounds 14-19, 20-25, and 27-29 were synthesized.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 581-584 
    ISSN: 0009-2940
    Keywords: Vinylferrocene ; Pd-catalyzed twofold and fourfold couplings ; Electron-donor-acceptor[2.2]paracyclophanes ; Charge transfer ; Cyclic voltammetry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As potential nonlinear optical material. 12-nitro-4,7-bis(2-ferrocenylvinyl)[2.2]paracyclophane (1) and 12-nitro-4,5,7,8-tetrakis(2-ferrocenylvinyl)[2.2]paracyclophane(2) have been synthesized by pd-catalyzed coupling reactions of vinylferrocene with the precursor cyclophanes 9 and 13, respectively. The absorption and electrochemical properties of 1 and 2 are also described.
    Additional Material: 1 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 519-526 
    ISSN: 0887-624X
    Keywords: cyclic oligomer ; ring-opening polymerization ; phenylphosphine oxide ; phosphorous ; MALDI-TOF-MS ; poly(arylene ether) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of cyclic(arylene ether) oligomers containing the phenylphosphine oxide moiety has been synthesized by reaction of bis(4-fluorophenyl)phenylphosphineoxide with dihydroxy compounds 1a-d as well as 1,2-dihydro-4-(4-hydroxyphenyl) (2H)phthalazin-1-one in DMF in the presence of anhydrous K2CO3 under high dilution conditions. These cyclic oligomers are amorphous and have high solubility in organic solvents. The MALDI-TOF-MS technique has been used as a powerful tool to analyze these cyclic systems. The cyclic(arylene ether) oligomers readily undergo anionic ring-opening polymerization in the melt at 350°C by using potassium 4,4′-biphenoxide as the initiator, affording linear, high molecular weight poly(arylene ether)s containing the phenylphosphine oxide moiety. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 519-526, 1998
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2333-2340 
    ISSN: 0887-624X
    Keywords: poly(1,6-heptadiyne)s ; electro-optics ; third-order nonlinearity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We utilized the metathesis reaction to synthesize a new type of multifunctional polymer that contains a conjugated backbone and a second-order NLO chromophore as a pendant group. The 1,6-heptadiyne derivatives bearing NLO chromophores were easily polymerized by using a metathesis catalyst to give corresponding polymers with large optical nonlinearities. Molecular structural characterizations for the resulting polymers were achieved by 1H- and 13C-NMR, FTIR, and UV-visible spectroscopies. Soluble polymers were obtained up to 72 mol % of chromophore monomer portion in the copolymer. These amorphous polymers exhibited good film-forming abilities and thermal stability. The electro-optic coefficient, r33, of the poled polymer films was in the range of 0.5-10.1 pm/V, and the nonresonant values of the third-order NLO coefficient, χ(3) was found to be about 10-11 esu. © 1996 John Wiley & Sons, Inc.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 2777-2786 
    ISSN: 0887-624X
    Keywords: aromatic thermotropic liquid crystalline polyesters ; nematic melts ; 2-(α-phenylisopropyl)hydroquinone ; 2,6-dihydroxynaphthalene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two series of new aromatic copolyesters have been synthesized and their properties including liquid crystallinity have been studied. The first series was synthesized by polymerizing mixtures of diacetates of 2-(α-phenylisopropyl)hydroquinone and 1,1′-biphenyl-4,4′-diol with terephthalic acid, and the second by polymerizing mixtures of diacetates of 2-(α-phenylisopropyl)hydroquinone and 2,6-dihydroxynaphthalene with terephthalic acid. These polyesters were characterized by differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray diffractomerty, and optical microscopy. The glass transition temperatures of the first series decrease from 167 to 138°C as one increases the content of the 1,1′-biphenyl-4,4′-diol unit to 50 mol %. The Tg values of the second series are slightly higher than those of the first series, and appear to be less dependent on their composition. The degree of crystallinity of the first series decreases rapidly by copolymerization, much faster than that of the second series. The melting points of the first series copolymers are significantly lower than those of the second series. All of the copolyesters reported in this investigation form nematic melts. The initial decomposition temperatures of the copolymers were higher than 450°C. It was confirmed that thermal stability of the homopolyester, PIBPL-1.00, containing the isopropylidene units is significantly improved when compared with that carrying benzylic hydrogens. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2777-2786, 1997
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2331-2338 
    ISSN: 0887-624X
    Keywords: poly(ether urethane) ; surface modification ; heparin immobilization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel poly(ether urethanes) containing diester groups in the side chains (PU) were synthesized from 4,4′-diphenylmethyl diisocyanate, polytetramethylene glycol, and diethyl bis(hydroxymethyl)malonate as a chain extender. The surface modification of the PU film was carried out by a hydrolysis reaction, poly(ethylene oxide) (PEO) grafting, and heparin immobilization, and the surface-modified PUs were then characterized by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, electron spectroscopy for chemical analysis (ESCA), and a contact angle goniometer. The concentration of carboxylic acid groups introduced on the PU surfaces as determined by the rhodamine interaction method was 61 nmol/cm2 when treated with 4N NaOH/methanol (1 : 2 v/v) for 30 min and subsequently with a citric acid-methanolic aqueous solution. The amounts of heparin coupled to the carboxyl groups on the PU surfaces and to the terminus amino groups on the PU-PEO were 0.92 and 0.84 μ g/cm2, respectively. There was almost no heparin released from the immobilized surface of a physiological solution for 100 h, thereby indicating the strong stability of immobilized heparin. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2331-2338, 1998
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