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31.
Michael Ruppel Dr. Dominik Lungerich Sabrina Sturm Dr. Rainer Lippert Dr. Frank Hampel Prof. Dr. Norbert Jux 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3287-3296
Tetraaryltetrabenzoporphyrins (TATBPs) show, due to their optoelectronic properties, rising potential as dyes in various fields of physical and biomedical sciences. However, unlike in the case of porphyrins, the potential structural diversity of TATBPs has been explored only to little extent, owed mainly to synthetic hurdles. Herein, we prepared a comprehensive library of 30 TATBPs and investigated their fundamental properties. We elucidated structural properties by X-ray crystallography and found explanations for physical properties such as solubility. Fundamental electronic aspects were studied by optical spectroscopy as well as by electrochemistry and brought in context to the stability of the molecules. Finally, we were able to develop a universal synthetic protocol, utilizing a readily established isoindole synthon, which gives TATBPs in high yields, regardless of the nature of the used arylaldehyde and without meticulous chromatographic purifications steps. This work serves as point of orientation for scientists, that aim to utilize these molecules in materials, nanotechnological, and biomedical applications. 相似文献
32.
In the last decades, the solid-waste management related to the extensively growing production of plastic materials, in concert with their durability, have stimulated increasing interest in biodegradable polymers. At present, a variety of biodegradable polymers has already been introduced onto the market and can now be competitive with non biodegradable thermoplastics in different fields (packaging, biomedical, textile, etc.). However, a significant economical effort is still directed in tailoring structural properties in order to further broaden the range of applications without impairing biodegradation. Improving the performance of biodegradable materials requires a good characterization of both physico-chemical and mechanical parameters. Polymer analysis can involve many different features including detailed characterization of chemical structures and compositions as well as average molecular mass determination. It is of outstanding importance in troubleshooting of a polymer manufacturing process and for quality control, especially in biomedical applications. This review describes recent trends in the structural characterization of biodegradable materials by modern mass spectrometry (MS). It provides an overview of the analytical tools used to evaluate their degradation. Several successful applications of MALDI-TOF MS (matrix assisted laser desorption ionization time of flight) and ESI MS (electrospray mass spectrometry) for the determination of the structural architecture of biodegradable macromolecules, including their topology, composition, chemical structure of the end groups have been reported. However, MS methodologies have been recently applied to evaluate the biodegradation of polymeric materials. ESI MS represents the most useful technique for characterizing water-soluble polymers possessing different end group structures, with the advantage of being easily interfaced with solution-based separation techniques such as high-performance liquid chromatography (HPLC). 相似文献
33.
Normal human dermal fibroblasts: proteomic analysis of cell layer and culture medium. 总被引:7,自引:0,他引:7
Federica Boraldi Luca Bini Sabrina Liberatori Alessandro Armini Vitaliano Pallini Roberta Tiozzo Ivonne Pasquali Ronchetti Daniela Quaglino 《Electrophoresis》2003,24(7-8):1292-1310
Proteins present within the cell layer and those released in the cell medium from in vitro cultured normal human dermal fibroblasts were separated and characterized in terms of their isoelectric point and molecular weight, by two-dimensional (2-D) gel electrophoresis. All spots in the synthetic gel were firstly analyzed by the Melanie 3 software and compared with those of breast cancer cells, colorectal epithelial cells, HL60, lymphoma cells, and platelets, already available on-line. From the identification of 144 spots from both the cell layer and the medium, we were able to recognize 89 different proteins, since a certain number of spots represented different isoforms of the same molecule. Identifications were performed by matching with on-line 2-D databases, and by matrix assisted laser-desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), in order to confirm the identification by matching, or to identify new proteins. The procedure we used allows (i) to design a highly reproducible reference map of the proteome of adult human normal fibroblasts in culture, (ii) to evaluate protein species produced in the cell layer as well as those released in the culture medium, and (iii) to compare data from gel matching with those obtained by MS. This work represents an essential step for a better knowledge of mesenchymal cells, given the widespread use of this cell type in both clinical and experimental investigations. 相似文献
34.
McCarron P Emteborg H Giddings SD Wright E Quilliam MA 《Analytical and bioanalytical chemistry》2011,400(3):847-858
A candidate certified reference material (CRM) for multiple shellfish toxins (domoic acid, okadaic acid and dinophysistoxins,
pectenotoxins, yessotoxin, azaspiracids and spirolides) has been prepared as a freeze-dried powder from mussel tissues (Mytilus edulis). Along with the certified values, the most important characteristics for a reference material to be fit-for-purpose are
homogeneity and stability. Acceptable between-bottle homogeneity was found for this CRM. Within-bottle homogeneity was assessed
using domoic acid, and it was shown that repeated subsampling of the CRM can be performed precisely down to 0.35 g. Both short-
and long-term stability studies carried out under isochronous conditions demonstrated excellent stability of the various toxins
present in the material. While degradation of some analytes was observed at +60°C in short-term studies, it was determined
that shipping at ambient temperature is adequate. No instability was detected in long-term stability studies, and it was shown
that the material can be held at +18°C safely for up to 1 year. To guarantee stability of the CRM over its lifetime the stock
will be maintained at −20°C. The results of the homogeneity and stability testing show that CRM–FDMT1 is appropriate for its
intended use in quality assurance and quality control of shellfish toxin analysis methods. 相似文献
35.
36.
Mustapha Raihane Valter Castelvetro Sabrina Bianchi Salima Atlas Bruno Ameduri 《Journal of polymer science. Part A, Polymer chemistry》2010,48(21):4900-4908
A novel copolymer of vinylidene cyanide (VCN) and 2,2,2‐trifluoroethyl methacrylate (MATRIF) was synthesized by bulk free radical process in a 52% yield from an equimolar comonomer feed. The copolymer's composition and microstructure were analyzed by FTIR, 1H‐ and 13C‐NMR spectroscopy, SEC, and elemental analysis. The reactivity ratios calculated from both the Q‐e Alfrey‐Price parameters and the Jenkins' Patterns Scheme indicate a tendency to alternation in the copolymerization, the latter method suggesting that MATRIF homopropagation be slightly favoured (rV = r12 = 0.1, rM = r21 = 0.3). The molar incorporation of VCN in the copolymer was only 42 mol % according to the 9.0 wt % nitrogen content determined by elemental analysis, in good agreement with the value obtained by 1H‐NMR. High‐resolution 1H and 13C‐NMR spectra were used to study the microstructure of the copolymer. As an example, the three well‐resolved carbonyl resonances in the 13C‐NMR spectrum were assigned to the MATRIF‐centered triads VMV, VMM, and MMM, respectively, (V and M stand for VCN and MATRIF, respectively). The presence of VCN dyads (e.g., in VVM and VVV sequences) was shown to be marginal or absent altogether. Thermogravimetric analysis of poly(VCN‐co‐MATRIF) copolymer showed good thermal stability, and its main pyrolytic degradation taking place only above 368 °C. A 4% weight loss at about 222 °C suggested the presence of a few VCN homodyads, possibly inducing thermal depolymerization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
37.
38.
The behavior of the symmetrical ethane-bridged bis(Zn porphyrin) (1) has been investigated at the air-water interface. The molecular organization of floating films of pure 1 and its mixture with amphiphilic substances, such as arachidic acid and n-octadecylamine, was inspected by means of surface pressure-area isotherms, Brewster angle microscopy and reflection spectroscopy in the UV-Vis region. The overall results suggest the presence in all cases of mainly the anti conformer of 1 even when the dimer was spread on pure water, through the ligation of water molecules to the zinc atoms in the axial positions. It was also demonstrated for the first time that the syn-to-anti conformational transition of the porphyrin dimer can be accelerated by the ligation of suitable amphiphiles even at the liquid-air interface. In particular, it is noted that n-octadecylamine, and arachidic acid (to a lesser extent), added to the system as amphiphiles, drive the syn ? anti equilibrium of 1 towards the anti form through the axial ligation of the amino or carboxylate group to the zinc atoms. 相似文献
39.
40.
A new functional group, the hydroxy group, was inserted into a Betti base by reaction with salicylaldehyde, and the naphthoxazine derivatives thus obtained were converted by ring-closure reactions with formaldehyde, acetaldehyde, propionaldehyde or phosgene to the corresponding naphth[1′2′:5,6][1,3]oxazino[3,2-c][1,3]benzoxazine derivatives. Further, the conformational analysis of these polycyclic compounds by NMR spectroscopy and an accompanying molecular modelling are reported; especially, both quantitative anisotropic ring current effects of the aromatic moieties in these compounds and steric substituent effects were employed to determine the stereochemistry of the naphthoxazinobenzoxazine derivatives. 相似文献