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EN
The samples of poly(n-propyl acrylate), PnPrA, and poly(isopropyl acrylate), PiPrA, were synthesized by free radical polymerization in solution (butan-2-one). The 100 MHz 13C NMR spectra of these homopolymers were recorded in two deuterated solvents: chloroform (CDCl3) and benzene (C6D6). In the spectra of both PnPrA and PiPrA recorded in CDCl3 the carbonyl signal was split at the level of configurational triads, while in C6D6 this signal revealed heptad splitting for PiPrA and pentad splitting for PnPrA.
PL
Próbki poli(akrylanu n-propylu), PnPrA, i poli(akrylanu izopropylu), PiPrA, otrzymano w polimeryzacji rodnikowej w roztworze butan-2-onu. Widma 100 MHz 13C NMR tych homopolimerów zarejestrowano w dwóch deuterowanych rozpuszczalnikach: chloroformie (CDCl3) i benzenie (C6D6). Na widmach PnPrA i PiPrA, zarejestrowanych w deuterowanym chloroformie, sygnał węgli karbonylowych (C=O) ulega rozszczepieniu na poziomie triad konfiguracyjnych, podczas gdy dla deuterowanego benzenu sygnał C=O PiPrA rozszczepia się na poziomie heptad, a dla PnPrA pentad konfiguracyjnych.
EN
Viscoelastic properties of polybutadiene are closely connected with the content and distribution of butadiene cis-1,4, trans-1,4 and 1,2 (vinyl) isomeric repeating units constituting the polymer chain, hence, there is a strong need to control them in order to obtain polybutadiene with desired properties. In this study we have examined influence of well-known polar modifiers, with respect to the complex type they form with the living center: Lewis bases (σ complex), Lewis acids (µ complex), mixture of Lewis base and Lewis acid (σ+µ complex) and acid-bases (σ–µ complex), on the kinetics of anionic polymerization of 1,3-butadiene and microstructure of the polymer formed.
PL
Lepkosprężyste właściwości polibutadienu są ściśle związane z zawartością i rozmieszczeniem izomerycznych, powtarzających się jednostek cis-1,4, trans-1,4 i 1,2 (winylowych) tworzących łańcuch polimerowy, stąd istnieje silna potrzeba ich kontrolowania, w celu uzyskania polibutadienu o pożądanych właściwościach. W pracy przebadano dobrze znane modyfikatory polarne, w odniesieniu do typu kompleksu jaki tworzą z centrum aktywnym: zasady Lewisa (kompleks σ), kwasy Lewisa (kompleks µ), mieszanina zasady i kwasu Lewisa (kompleks σ+µ) i kwasowo-zasadowe (kompleks σ–µ), na kinetykę polimeryzacji anionowej 1,3-butadienu i mikrostrukturę tworzonego polimeru.
EN
The samples of poly(n-propyl acrylate), PnPrA, and poly(isopropyl acrylate), PiPrA, were synthesized by free radical polymerization in solution (butan-2-one). The 100 MHz 13C NMR spectra of these homopolymers were recorded in two deuterated solvents: chloroform (CDCl3) and benzene (C6D6). In the PnPrA spectra, the backbone β-methylene carbon signal (β-CH2) (33.0 - 36.5 ppm) was split up to configurational hexads for CDCl3 and C6D6. In the PiPrA spectra, the β-CH2 signal (32.5 - 36.5 ppm) was split up to configurational hexads in both solvents.
PL
Próbki poli(akrylanu n-propylu), PnPrA, i poli(akrylanu izopropylu), PiPrA, otrzymano w polimeryzacji rodnikowej w roztworze. Widma 100 MHz 13C NMR tych homopolimerów zarejestrowano w dwóch deuterowanych rozpuszczalnikach: chloroformie (CDCl3) i benzenie (C6D6). Na widmach PnPrA, zarejestrowanych w deuterowanym chloroformie i benzenie sygnał, węgli metylenowych (β-CH2) (33,0 - 36,5 ppm) ulega rozszczepieniu się na poziomie heksad konfiguracyjnych, natomiast sygnał β-CH2 (32,5 - 36,5 ppm) poli(akrylanu izopropylu) rozszczepia się na poziomie heksad konfiguracyjnych.
EN
The microstructure characterization of two butyl acrylate homopolymers poly(isobutyl acrylate), PiBuA and poly(sec-butyl acrylate), PsBuA, prepared by anionic polymerization, was investigated by ¹³C NMR spectroscopy. It was found that the carbonyl signal in the 100 MHz ¹³C NMR spectra of both homopolymers was sensitive to configurational effects and provided sufficient resolution to perform detailed analysis of sequence distribution at the triad/pentad level. The line assignments can be verified by spectral simulation based on incremental calculation of the chemical shifts of individual sequences.
PL
Wykorzystując spektroskopię ¹³C NMR przeprowadzono charakterystykę mikrostrukturalną dwóch homopolimerów akrylowych, poli(akrylanu izobutylu), PiBuA, oraz poli(akrylanu sec-butylu), PsBuA, uzyskanych na drodze polimeryzacji anionowej. Stwierdzono, że sygnał karbonylowy obydwu homopolimerów jest czuły na efekty konfiguracyjne, a rozdzielczość sygnału C=O pozwala na analizę rozkładu sekwencji na poziomie triad i pentad konfiguracyjnych. Przypisanie sygnałów zostało zweryfikowane przez komputerową symulację widma opartą na inkrementalnych obliczeniach przesunięć chemicznych poszczególnych sekwencji.
PL
Dokonano przeglądu metod polimeryzacji butadienu i izoprenu oraz wpływu parametrów tego procesu na mikrostrukturę i właściwości fizykochemiczne otrzymywanych homopolimerów oraz kopolimerów ze styrenem. Szczegółowo omówiono możliwości sterowania strukturą łańcucha powstającego w polimeryzacji anionowej, zwłaszcza przy zastosowaniu modyfikatorów polarnych.
EN
A review, with 49 refs., of methods for controlling chain structures formed during anionic polymerization in the presence of polar modifiers.
PL
Dokonano przeglądu i klasyfikacji układów inicjujących stosowanych w procesie polimeryzacji anionowej, zdolnych do sterowania mikrostrukturą łańcucha polibutadienu (BR), poliizoprenu (IR), a także kopolimeru butadienu (SBR) lub izoprenu (SIR) ze styrenem. Rozpatrzono wpływ modyfikatorów polarnych z grupy zasad i kwasów Lewisa na szybkość procesu polimeryzacji, zawartość struktur izomerycznych butadienu i izoprenu oraz rozkład sekwencji jednostek monomerycznych w ich kopolimerach ze styrenem.
EN
A review, with 98 refs., of acidic, alk. and mixed initiator systems used in anionic polymerization for controlling the microstructure of butadiene and isoprene homopolymers (butadiene and isoprene rubbers) and copolymers with styrene (styrene-butadiene and styrene-isoprene rubbers).
EN
Microstructural analysis of macromolecular chain of poly(n-butyl methacrylate) was performed using 13C NMR spectroscopy. The samples of PnBuMA, were synthesized in two ways: free radical polymerization and anionic polymerization. The 100 MHz 13C NMR spectra of this homopolymer were recorded in deutereted chloroform. The carbonyl signal in the region from 175.5 to 178.5 ppm was found to be sensitive to chain configuration at the heptad level, while the β-methylene signal of the carbon chain (49.0-55.0 ppm) was split up to configurational hexads.
PL
Badania mikrostruktury poli(metakrylanu n-butylu) przeprowadzono z wykorzystaniem spektroskopii 13C NMR. Próbki PnBuMA uzyskano na drodze polimeryzacji wolnorodnikowej i anionowej. Widma 100 MHz 13C NMR homopolimeru metakrylanu n-butylu zarejestrowano w deuterowanym chloroformie. Sygnał karbonylowy w zakresie od 175,5 do 178,5 ppm, jest czuły na efekty konfiguracyjne na poziomie heptad, natomiast sygnał węgli metylenowych z łańcucha głównego (49,0 - 55,0 ppm) rozszczepia się na poziomie heksad konfiguracyjnych.
8
Content available remote Synteza, badania NMR i DSC kopolimeru metakrylanu metylu z akrylanem n-propylu
PL
Próbki polimerów: poli(akrylanu n-propylu), poli(metakrylanu metylu) i poli(metakrylanu metylu-co-akrylanu n-propylu) otrzymano w wolnorodnikowej polimeryzacji w roztworze, uzyskując łańcuch o dominacji struktur syndiotaktycznych. Widma 400 MHz ¹H NMR i 100 MHz ¹³C NMR zsyntezowanych polimerów zarejestrowano w deuterowanym benzenie. Przypisano sygnały rezonansowe protonom i węglom z łańcucha polimerowego. Dla otrzymanych próbek wykonano pomiary temperatury zeszklenia, Tg, przy użyciu skaningowej kalorymetrii różnicowej, DSC.
EN
Poly(n-propyl acrylate), poly(methyl methacrylate) and poly(methyl acrylate-co-n-propyl acrylate), were synthesized by free radical polymerization in solution, obtaining samples containing predominantly syndiotactic structure. The 400 MHz ¹H NMR and 100 MHz ¹³C NMR spectra of these polymers were recorded in deutereted benzene. The resonance signals were assigned to protons and carbons from polymer chain. The polymer samples were also analyzed using differential scanning calorimetry, DSC, determining their glass transition temperatures, Tg.
EN
A series of copolymer samples of methyl methacrylate and isopropyl acrylate of different composition were synthesized by radical polymerization. Their 400 MHz 1H NMR permitted determination of the copolymer composition while the 100 MHz 13C NMR spectra provided the insight into the chain microstructure at the level of configurational-compositional pentads. DSC measurements were performed to relate the sequence distribution with the mechanical properties of the copolymer samples.
EN
100 MHz 13C NMR spectra of poly(tert-butyl methacrylate) homopolymer, PtBMA, exhibit sensitivity on the chain tacticity at the pentad level for the carbonyl signal and at triad level for the backbone quaternary carbon. Detailed analysis of these regions can provide information on distribution of configurational sequences. The line assignments can be verified by spectral simulation based on incremental calculation of the chemical shifts of individual sequences.
EN
Microstructure of copolymers of two methacrylate monomers are difficult to analyze by 13C NMR spectroscopy since the region of the carbonyl signals, usually utilized for this purpose, is relatively narrow and the lines split due to different sequences are strongly superimposed. The spectra of the two respective homopolymers indicate that both monomers introduce configurational effects, hence the copolymer microstructure should be described in terms of distribution of configurational-compositional sequences. It was shown that for the investigated copolymer of n-butyl methacrylate and methyl methacrylate such analysis can be performed at the triad level.
EN
The objective of this study was to explore the possibility of combining headspace gas chromatography with mass spectrometric detection (HS-GC-MS) and 13C NMR spectroscopy to enhance the detectability of components of the essential oils of medicinal plants of the Salvia genus. Preliminary investigations were performed with two sage species, Salvia lavandulifolia and Salvia triloba, known for particularly abundant yields of their respective essential oils. By use of HS-GC-MS, characteristic fingerprints of the volatile fractions were obtained for plant species from two different vegetation seasons (2007 and 2008). Partial identification of the components of these volatile fractions was performed, and comparison of the chromatographic fingerprints confirmed seasonal fingerprint similarity within the same species. Preliminary 13C NMR measurements resulted in well shaped spectra with an abundance of regularly distributed signals. This suggested the possibility of using 13C NMR spectroscopy in phytochemical research, in parallel with HS-GC-MS, to enhance the detectability of volatile components of plant species belonging to this genus.
13
Content available remote On the spontaneous condensation of profens, with ketoprofen as an example
EN
In a series of recently published full-length papers and short communications we attempted to gain deeper insight into elementary reactions which might contribute to the non-linear nature of the spontaneous chiral conversion of low-molecular-weight carboxylic acids. Earlier, we succeeded in demonstrating that amino acids and hydroxy acids can undergo spontaneous peptidization and spontaneous esterification (both regarded as condensation), respectively, when dissolved in 70% aqueous ethanol. In this study we provide experimental proof from thin-layer chromatography and 13 C NMR spectroscopy of spontaneous condensation of profens, with ketoprofen as an example. It can be expected that other profen drugs undergo an analogous condensation. In the future, an analogy between the ability of amino acids, hydroxy acids, and profens to undergo spontaneous peptidization or condensation (as reported in our papers), and the ability of selected organosilanols to undergo the spontaneous oscillatory condensation (as reported elsewhere), might prove essential for better understanding of detailed mechanism of the spontaneous oscillatory in-vitro chiral conversion of the selected low-molecular-weight carboxylic acids.
PL
Spektroskopia 13C NMR jest doskonałym narzędziem do badania mikrostruktury łańcucha polimerowego, gdyż pozwala obserwować atomy węgla oraz ich sąsiadów od "wewnątrz" makrocząsteczki. Dokładne zdefiniowanie mikrostruktury pozwala na "sterowanie" budową łańcucha, a co za tym idzie otrzymywanie polimeru o żądanych właściwościach fizykochemicznych i mechanicznych.
15
Content available remote On the spontaneous condensation of selected hydroxy acids
EN
In a previous study we provided thin-layer chromatographic, polarimetric, and other experimental evidence that phenylglycine can undergo easy spontaneous peptidization in abiotic aqueous media. From our unpublished results it is apparent that this behaviour is also characteristic of some other amino acids (e.g., alanine and phenylalanine). It seems highly probable that this abiotic peptidization of amino acids dissolved in aqueous media is directly linked to their ability to undergo spontaneous oscillatory chiral conversion. In our earlier research it was also shown that spontaneous oscillatory chiral conversion was characteristic not only of amino acids but also of several other classes of carboxylic acid, including profen drugs and hydroxy acids. We therefore decided to check whether selected chiral hydroxy acids — lactic acid and mandelic acid — previously recognized for their ability to undergo spontaneous oscillatory chiral conversion, could also furnish the respective polyacids. Condensation of hydroxy acids can be viewed as a reaction fully analogous with peptidization of amino acids and, hence, it seemed to us highly probable that it also can be triggered by oscillatory chiral conversion. In our study, we used thin-layer chromatography and 13 C NMR spectroscopy to check whether formation of polylactic acid and polymandelic acid occurred in stored solutions of lactic and mandelic acids. By means of polarimetry with continuous recording we provided experimental evidence that all three hydroxy acids investigated (i.e. L -(+)-lactic acid, S -(+)-mandelic acid, and R -(−)-mandelic acid) undergo continuous chiral conversion. From the thin-layer chromatographic results obtained it was apparent that — similar to the spontaneous and instantaneous peptidization of amino acids — the hydroxy acids investigated also undergo easy condensation to form the respective polyacids. 13 C NMR spectroscopy provided additional experimental confirmation of this.
EN
The permanent demand for novel drugs by the pharmaceutical industry results in a variety of novel methods for drug discovery. Combinatorial methods are a novel direction of drug research based on synthesis of large number of compounds in the hope of finding interesting drug-like molecules. In dynamic combinatorial chemistry (DCC) an enzyme is used to control the synthetic path and increase the proportion of the drug-like molecules in the reaction mixture. Because the mixture formed by the reaction is complex, analytical procedures limit possible application of the method. In the work discussed in this publication HPLC was coupled with 13C NMR for analysis of a DCC system. Transamidation controlled by use of Candida rugosa lipase was compared with the reaction without the enzyme. This enabled us to show that the enzyme-promoted reaction favoured the amine with the lowest nucleophilicity.
EN
DSC thermogrammes of mixtures of poly(methyl methacrylate-co-ethyl acrylate), PMMA-EA, of different microstructure of macromolecular chains, exhibit two glass transition temperatures, Tg, indicating the presence of two phases. In one phase the copolymer chains are compatible with long blocks of ethyl acrylate and the second phase is very rich in long chains of methyl methacrylate. Based on the 13C NMR results for compositional diads distribution and DSC data, a miscibility line can be drawn when the results are presented in a form of a triangular diagram.
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