Since their addition to the polymer-architecture portfolio, gradient copolymers have attracted significant attention. Up to now, however, the existence of the intramolecular composition gradient must have been ascertained by sampling during living copolymerization because a reliable method for the detection of the composition gradient in the finalized copolymer had not been established yet. Here we show that MALDI-ToF mass spectrometry not only identifies imperfect, i.e. prematurely terminated copolymers but these copolymers can be used as "time capsules" which provide information on composition evolution and the intramolecular composition gradient.
- Publikační typ
- časopisecké články MeSH
Alginate gels are an outstanding biomaterial widely applicable in tissue engineering, medicine, and pharmacy for cell transplantation, wound healing and efficient bioactive agent delivery, respectively. This contribution provides new and comprehensive insight into the atomic-resolution structure and dynamics of polyvalent ion-cross-linked alginate gels in microbead formulations. By applying various advanced solid-state NMR (ssNMR) spectroscopy techniques, we verified the homogeneous distribution of the cross-linking ions in the alginate gels and the high degree of ion exchange. We also established that the two-component character of the alginate gels arises from the concentration fluctuations of residual water molecules that are preferentially localized along polymer chains containing abundant mannuronic acid (M) residues. These hydrated M-rich blocks tend to self-aggregate into subnanometer domains. The resulting coexistence of two types of alginate chains differing in segmental dynamics was revealed by 1H-13C dipolar profile analysis, which indicated that the average fluctuation angles of the stiff and mobile alginate segments were about 5-9° or 30°, respectively. Next, the 13C CP/MAS NMR spectra indicated that the alginate polymer microstructure was strongly dependent on the type of cross-linking ion. The polymer chain regularity was determined to systematically decrease as the cross-linking ion radius decreased. Consistent with the 1H-1H correlation spectra, regular structures were found for the gels cross-linked by relatively large alkaline earth cations (Ba2+, Sr2+, or Ca2+), whereas the alginate chains cross-linked by bivalent transition metal ions (Zn2+) and trivalent metal cations (Al3+) exhibited significant irregularities. Notably, however, the observed disordering of the alginate chains was exclusively attributed to the M residues, whereas the structurally well-defined gels all contained guluronic acid (G) residues. Therefore, a key role of the units in M-rich blocks as mediators promoting the self-assembly of alginate chains was experimentally confirmed. Finally, combining 2D 27Al 3Q/MAS NMR spectroscopy with density functional theory (DFT) calculations provided previously unreported insight into the structure of the Al3+ cross-linking centers. Notably, even with a low residual amount of water, these cross-linking units adopt exclusively 6-fold octahedral coordination and exhibit significant motion, which considerably reduces quadrupolar coupling constants. Thus, the experimental strategy presented in this study provides a new perspective on cross-linked alginate structure and dynamics for which high-quality diffraction data at the atomic resolution level are inherently unavailable.
Plausible calf-thymus DNA molecular weight distribution can be obtained by size-exclusion chromatography with dual low-angle light scattering/refractometric detection at sufficiently low flow rate. The distribution extends over three decades of molecular weight and is characterized by weight average molecular weight M(w) = 8418000 and polydispersity index M(w)/M(n) = 5.2. After strongly scattering impurities had been removed from the sample using adsorption properties of the 3 mum mixed-cellulose-ester filter membranes, static light-scattering measurement in flow injection mode was feasible and gave M(w) = 8580000, corroborating the veracity of SEC results.
- MeSH
- DNA analýza chemie MeSH
- gelová chromatografie metody MeSH
- molekulová hmotnost MeSH
- radiační rozptyl MeSH
- skot MeSH
- světlo MeSH
- zvířata MeSH
- Check Tag
- skot MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- srovnávací studie MeSH
A general relationship is derived for the abundance of an imperfect dendrimer with a given number of missing constitutional repeating units in the two outmost layers. The relationship is used in the interpretation of the MALDI TOF mass spectrum of the second-generation carbosilane dendrimer prepared by the iterative divergent method. The model quantitatively describes the spectrum of the dendrimer and correctly predicts the MALDI TOF mass spectrum of its first-generation precursor. Thus, the use of well-resolved MALDI TOF mass spectra for assessing the purity of low-generation dendrimers with uniform end groups is substantiated for carbosilane dendrimers and to lesser extent for dendrimers in general.
- Klíčová slova
- CANDESARTAN CILEXETIL,
- MeSH
- antihypertenziva aplikace a dávkování škodlivé účinky terapeutické užití MeSH
- inhibitory ACE terapeutické užití MeSH
- kardiovaskulární nemoci farmakoterapie MeSH
- krevní tlak účinky záření MeSH
- renin-angiotensin systém metabolismus MeSH
- Publikační typ
- kongresy MeSH
1. vyd. nečísl. strany : fot.,lit. ; 20 cm
- MeSH
- homosexualita MeSH
- sexuálně přenosné nemoci prevence a kontrola MeSH
- Publikační typ
- populární práce MeSH
- Konspekt
- Patologie. Klinická medicína
- NLK Obory
- sexuologie
Developments in obstetrics and gynecology ; Vol. 3
423 s. : il.
- Konspekt
- Lékařské vědy. Lékařství
- NLK Obory
- gynekologie a porodnictví
- endokrinologie
- gynekologie a porodnictví
