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61.
Pulkkinen M Palmgrén JJ Auriola S Malin M Seppälä J Järvinen K 《Rapid communications in mass spectrometry : RCM》2008,22(2):121-129
This paper describes a straightforward and rapid on-line characterization using high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC/ESI-MS(n)) of the enzymatic degradation products of 2,2'-bis(2-oxazoline)-linked poly-epsilon-caprolactone (PCL-O). These new PCL-O polymers are expected to be used in a variety of pharmaceutical and biomedical applications since they are degraded enzymatically by surface erosion. PCL-O was polymerized in a three-step reaction and characterized by (1)H-NMR and size-exclusion chromatography (SEC). Solvent cast polymer films were exposed to enzymatic degradation in phosphate buffer (pH 7.5, 1% pancreatin). The enzymatic degradation of the polymer produced a wide variety of water-soluble oligomers which were separated and identified by HPLC/ESI-MS(n). Optimization of the gradient HPLC method resulted in effective separation of the oligomers. Furthermore, specific structures of the oligomers were clearly identified by tandem mass spectrometry. According to these results, ester bonds seem to be most sensitive to enzymatic degradation and, correspondingly, pancreatic lipase seems to be mainly responsible for the enzymatic erosion of the PCL-O films. This novel mass spectrometric method provides important knowledge about the enzymatic degradation process and structure of the polymer which is difficult to ascertain by other conventional methods. 相似文献
62.
Ruuska H Arola E Kannus K Rantala TT Valkealahti S 《The Journal of chemical physics》2008,128(6):064109
Feasibility of density functional theory (DFT) to predict dielectric properties such as polarizability of saturated polymers is investigated. Small saturated molecules, methane and propane, which is a monomer of polypropylene chain, are used in testing the methods. Results for polarizabilities based on several density functionals together with different basis sets are compared and contrasted with each other, with results by Hartree-Fock and second-order Moller-Plesset perturbation theory, as well as experimental data. The generalized gradient approximation PW91 method together with the 6-311++G(**) basis set is found to be the most suitable method, in terms of sufficient accuracy and computational efficiency, to calculate polarizabilities for large oligomers of polypropylene. The dielectric constant is then determined using the calculated polarizabilities and the Clausius-Mossotti equation. The molecular DFT methods at the PW916-311++G(**) level together with the Clausius-Mossotti equation give dielectric constants for saturated polymers such as polypropylene in good accordance with the experimental values. 相似文献
63.
Summary A bounded, not necessarily everywhere defined, nonnegative operator A in a Hilbert space <InlineEquation ID=IE"1"><EquationSource Format="TEX"><![CDATA[<InlineEquation ID=IE"2"><EquationSource
Format="TEX"><![CDATA[$]]></EquationSource></InlineEquation>]]></EquationSource></InlineEquation>\mathfrak{H}$ is assumed
to intertwine in a certain sense two bounded everywhere defined operators B and C. If the range of A is provided with a natural inner product then the operators B and C induce two new operators on the completion space. This construction is used to show the existence of selfadjoint and nonnegative
extensions of B*A and C*A. 相似文献
64.
Microbiological analyses are carried out on clinical, food, feed and environmental samples. The aims of the analyses are diagnostic
or estimation of the safety or the quality of the sample. Important decisions are made on the basis of microbiological analyses.
Little attention, however, is paid to the uncertainty of measurement of microbiological analyses. In microbiological cultivation
techniques the result is obtained by counting individual objects. The normally low number of counted objects strongly affects
the result of the analysis and its uncertainty. Because of the importance of the particle statistical variation to the uncertainty,
the approaches developed for chemical analyses are not directly applicable to microbiology. This paper discusses microbial
analyses and describes a novel guidance document for the estimation of measurement uncertainty in culturing methods [1].
Received: 7 October 2000 Accepted: 8 March 2001 相似文献
65.
66.
Parkkila S Vullo D Maresca A Carta F Scozzafava A Supuran CT 《Chemical communications (Cambridge, England)》2012,48(29):3551-3553
Acetoacetic acid and R-3-hydroxy-butyric acid (BHB) are "ketone bodies", metabolites produced during the ketogenic diet. We discovered that they inhibit in the submicromolar-micromolar range several carbonic anhydrase (CA, EC 4.2.1.1) isoforms involved in relevant physiologic processes such as lipogenesis and tumorigenesis. The BHB fragment is also present in the molecules of most statins, widely used drugs for inhibiting cholesterol biosynthesis through the 3-hydroxy-3-methyl-glutaryl-CoA reductase pathway. Three such statins, atorvastatin, fluvastatin and rosuvastatin, showed submicromolar-low nanomolar inhibition of the fifteen human isoforms hCA I-XIV. Our data point out that in addition to their cholesterol lowering properties, these drugs may exert a therapeutic effect by inhibiting lipogenesis through mitochondrial CA inhibition. The statins are also low nanomolar inhibitors of the tumor-associated isoforms CA IX and XII. Based on the BHB/statin scaffolds, antiepileptic, antiobesity and antitumor compounds with higher affinity for the various CA isoforms involved in epileptogenesis (CA VA, VB, VII), lipogenesis (CA III, CA VA, CA VB) and tumorigenesis (CA IX and CA XII) may be designed. 相似文献
67.
Seppo I. Pennanen 《合成通讯》2013,43(12):1063-1066
The synthesis of 4-substituted 2(5H)-furanones via organosilicon intermediates has been reported from this laboratory.1 This method gave possibilities to extend the synthesis to include 2-pyrone species (e. g. 1), which are structure units of some natural products. 相似文献
68.
Pekka Keski‐Rahkonen Kaisa Huhtinen Reena Desai D. Tim Harwood David J. Handelsman Matti Poutanen Seppo Auriola 《Journal of mass spectrometry : JMS》2013,48(9):1050-1058
Accurate measurement of estradiol (E2) is important in clinical diagnostics and research. High sensitivity methods are critical for specimens with E2 concentrations at low picomolar levels, such as serum of men, postmenopausal women and children. Achieving the required assay performance with LC–MS is challenging due to the non‐polar structure and low proton affinity of E2. Previous studies suggest that ionization has a major role for the performance of E2 measurement, but comparisons of different ionization techniques for the analysis of clinical samples are not available. In this study, female serum and endometrium tissue samples were used to compare electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) in both polarities. APPI was found to have the most potential for E2 analysis, with a quantification limit of 1 fmol on‐column. APCI and ESI could be employed in negative polarity, although being slightly less sensitive than APPI. In the presence of biological background, ESI was found to be highly susceptible to ion suppression, while APCI and APPI were largely unaffected by the sample matrix. Irrespective of the ionization technique, background interferences were observed when using the multiple reaction monitoring transitions commonly employed for E2 (m/z 271 > 159; m/z 255 > 145). These unidentified interferences were most severe in serum samples, varied in intensity between ionization techniques and required efficient chromatographic separation in order to achieve specificity for E2. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
69.
Estimation of the uncertainty of microbiological viable counts by the statistical analysis of series of observations is impractical because the observed value, the number of colonies, usually determines a large share of the uncertainty. Every test result, therefore, has a unique uncertainty and no general method-specific values exist. The most practical ways to estimate the uncertainty are based on mathematical models and assumed statistical distributions where the observed value is a significant parameter. The article describes the traditional solution based on the Poisson distribution and more advanced models based on the negative binomial distribution. The latter model is capable of combining technical and procedural components of uncertainty with the inevitable random scatter of microbial suspensions. The additional uncertainty due to subsampling in the confirmation of presumptive positives is estimated with the help of a binomial model. Traceability issues are discussed.Presented at the Metro Trade Workshop on Traceability and Measurement Uncertainty in Testing, 30–31 January 2003, Berlin, Germany 相似文献
70.
Kirsi S. Mikkonen Jasna S. Stevanic Catherine Joly Patrice Dole Kari Pirkkalainen Ritva Serimaa Lennart Salmén Maija Tenkanen 《Cellulose (London, England)》2011,18(3):713-726
Two future wood biorefinery products, spruce galactoglucomannans (GGM) and microfibrillated spruce wood cellulose (MFC), were
mixed to form composite films. The films were plasticized with different amounts of glycerol, and the preparation of films
was successful even with low glycerol contents. The film properties were studied using optical microscopy and scanning electron
microscopy, x-ray diffraction, water sorption, dielectric analysis, moisture scanning dynamic mechanical analysis, and tensile
testing. The addition of MFC clearly affected the properties of the films by decreasing the moisture uptake and increasing
the relative humidity of softening of the films and by increasing the glass transition temperature, tensile strength, and
Young’s modulus of the films. The effect of MFC addition on the tensile properties of films was emphasized at low glycerol
contents. The addition of MFC did not affect the degree of crystallinity of GGM in the films, which was between 20 and 25%.
MFC can be efficiently used as reinforcement of GGM films to form wood-based composite materials and to prepare GGM-based
films and coatings with low plasticizer content. 相似文献