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91.
92.
The value and limitations of differential scanning calorimetry in the assessment of high-purity substances has been examined. In favorable cases, good agreement has been secured for polycyclic hydrocarbons between DSC purity values and GC assay values. For some halogenated benzoic acids, used as microanalytical reference standards, good agreement has been obtained between DSC purity values and acid—base titration results. DSC studies on cholesterol and urea, which have limited thermal stability, are presented. With the available instrument and technique, the practical upper limit of absolute DSC purity values may be 99.95 mole%, although higher numerical values can be obtained. Because the DSC technique is “blind” to equilibrium solid solution formation, DSC values should not be used as a sole criterion of purity; this recommendation is of special importance for compounds purified by fractional solidification processes. 相似文献
93.
G. Bonn H. Binder H. Leonhard O. Bobleter 《Monatshefte für Chemie / Chemical Monthly》1985,116(8-9):961-971
The alkaline degradation of cellobiose by 0.01 to 0.1N NaOH at temperatures between 60 and 85°C was studied. At the same time the formation of glucose and fructose was analyzed. At lower alkali concentrations, the production of acidic compounds lowered thepH to such an extent that the hydrolyzing reaction ceased within a relatively short time. At higher alkali concentrations thepH change is much smaller and first order reaction rates of the cellobiose degradation were obtained. Through the application of a simplified reaction mechanism the consecutive reactions of the glucose and fructose formation were evaluated mathematically.Dedicated to Prof. Dr.H. Tuppy on the occasion of his 60th birthday. 相似文献
94.
We present investigations of the transient photoconductivity and recombination dynamics of quasifree electrons in liquid n-hexane and cyclohexane performed using terahertz time-domain spectroscopy (THz-TDS). Quasifree electrons are generated by two-photon photoionization of the liquid using a femtosecond ultraviolet pulse, and the resulting changes in the complex conductivity are probed by a THz electromagnetic pulse at a variable delay. The detection of time-domain wave forms of the THz electric field permits the direct determination of both the real and the imaginary part of the conductivity of the electrons over a wide frequency range. The change in conductivity can be described by the Drude model, thus yielding the quasifree electron density and scattering time. The electron density is found to decay on a time scale of a few hundred picoseconds, which becomes shorter with increasing excitation density. The dynamics can be described by a model that assumes nongeminate recombination between electrons and positive ions. In addition, a strong dependence of the quasifree electron density on temperature is observed, in agreement with a two-state model in which the electron may exist in either a quasifree or a bound state. 相似文献
95.
Munazza Raza Mirza Matthias Rainer Shahid Duran Syed Tarique Moin M. Iqbal Choudhary Günther K. Bonn 《Biomedical chromatography : BMC》2019,33(9)
A poly(dibenzo‐18‐crown‐6) was used as a new solid‐phase extraction material for the selective enrichment of phosphopeptides. Isolation of phosphopeptides was achieved based on specific ionic interactions between poly(dibenzo‐18‐crown‐6) and the phosphate group of phosphopeptides. Thus, a method was developed and optimized, including loading, washing and elution steps, for the selective enrichment of phosphopeptides. To assess this potential, tryptic digest of three proteins (α‐ casein, β‐casein and ovalbumin) was applied on poly(dibenzo‐18‐crown‐6). The nonspecific products were removed by centrifugation and washing. The spectrometric analysis was performed using matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. Highly selective enrichment of both mono‐ and multiphosphorylated peptides was achieved using poly(dibenzo‐18‐crown‐6) as solid‐phase extraction material with minimum interference from nonspecific compounds. Furthermore, evaluation of the efficiency of the poly(dibenzo‐18‐crown‐6) was performed by applying the digest of egg white. Finally, quantum mechanical calculations were performed to calculate the binding energies to predict the affinity between poly(dibenzo‐18‐crown‐6) and various ligands. The newly identified solid‐phase extraction material was found to be a highly efficient tool for phosphopeptide recovery from tryptic digest of proteins. 相似文献
96.
97.
98.
Michael Taylor Fabio Simoes James Smith Sivaneswary Genapathy Anne Canning Marina Lledos Weng C. Chan Chris Denning David J. Scurr Rory T. Steven Steve J. Spencer Alexander G. Shard Morgan R. Alexander Mischa Zelzer 《Surface and interface analysis : SIA》2022,54(4):417-432
Peptide-coated surfaces are widely employed in biomaterial design, but quantifiable correlation between surface composition and biological response is challenging due to, for example, instrumental limitations, a lack of suitable model surfaces or limitations in quantitatively correlating data from different surface analytical techniques. Here, we first establish a reference material that allows control over amino acid content. Reversible addition-fragmentation chain-transfer (RAFT) polymerisation is used to prepare a copolymer containing alkyne and furan units with well-defined chain length and composition. Huisgen Cu(I)-catalysed azide-alkyne cycloaddition reaction is used to attach the model azido-polyethyleneglycol-amide-modified pentafluoro-l -phenylalanine to the polymer. Different compositional ratios of the polymer provide a surface with varying amino acid content that is analysed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Nitrogen-related signals are compared with fluorine signals from both techniques. Fluorine and nitrogen signals from both techniques are found to be related to the copolymer compositions, but the homopolymer data deviate from this trend. The approach is then translated to a heparin-binding peptide that supports cell adhesion. Human embryonic stem cells cultured on copolymer surfaces presenting different amounts of heparin-binding peptide show strong cell growth while maintaining pluripotency after 72 h of culture. The early cell adhesion at 24 h can be correlated to the logarithm of the normalised CH4N+ ion intensity from ToF-SIMS data, which is established as a suitable and generalisable marker ion for amino acids and peptides. This work contributes to the ability to use ToF-SIMS in a more quantitative manner for the analysis of amino acid and peptide surfaces. 相似文献
99.
Bonn B Leandersson C Fontaine F Zamora I 《Rapid communications in mass spectrometry : RCM》2010,24(21):3127-3138
The identification of metabolites is almost exclusively done with liquid chromatography/tandem mass spectrometry (LC/MSMS) and despite the enormous progress in the development of these techniques and software for handling of data this is a time-consuming task. In this study the use of quadrupole time-of-flight (QTOF)-generated MS(E) and MS/MS data were compared with respect to rationalization of metabolites. In addition Mass-MetaSite, a semi-automated software for metabolite identification, was evaluated. The program combines the information from MS raw data, in the form of collision-induced dissociation spectra, with a prediction of the site of metabolism in order to assign the structure of a metabolite. The aim of the software is to mimic the rationalization of fragment ions performed by a biotransformation scientist in the process of structural elucidation. For this evaluation, metabolite identification in human liver microsomes was accomplished for 19 commercially available compounds and 15 in-house compounds. The results were very encouraging and for 96% of the metabolites the same structures were assigned using MS(E) compared with MSMS acquired data. The possibility of using MS(E) could considerably reduce the analysis time. Moreover, Mass-MetaSite performed well and the correct assigned structure, compared to manual inspection of the data, was picked in the first rank in ~80% of the cases. In conclusion MS(E) could be successfully used for metabolite identification in order to reduce time of analysis and Mass-MetaSite could alleviate the work of a biotransformation scientist and decrease the workload by assigning the structure for a majority of the metabolites. 相似文献
100.
Alexander Fabian Le Blanc Christiane Albrecht Tomas Bonn Peter Fechner Günther Proll Florian Pr?ll Mats Carlquist Günter Gauglitz 《Analytical and bioanalytical chemistry》2009,395(6):1769-1776
A novel combined procedure for estrogen-affinity purification and labelling of estrogen receptor α ligand-binding domain with
Cy™ 5.5 cystein reactive dye was established. By using this procedure, mainly functional proteins are recovered. It can be
easily adapted to a large variety of other proteins for which ligand-coated affinity materials are available. The labelled
receptor was used in a total internal reflection fluorescence-based binding inhibition assay for determination of the impact
of pollutants in river water on the receptor. The great advantage compared to conventional methods is that the total effect
on the receptor is measured instead of concentrations of single compounds and that even currently unknown ligands are found
as well. Therefore, the obtained signal is related to the response of the organism, which is exposed to the water. The limit
of detection was found to be 0.139 nM of estradiol equivalents. The assay also provides a highly sensitive tool for pharmaceutical
research and can be adapted to diagnostic applications.
相似文献