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201.
Possible applications of solid-state NMR in studies on polypeptides and proteins are presented. Several examples of 13-C CP/MAS NMR spectra are discussed in relation to model compounds and polypeptides from various sources. A comparison is made with vibrational spectroscopic methods. It is concluded that the CP/MAS NMR method is especially useful in elucidating secondary structures in the unperturbed state, and, thus, may also be useful in the study of various conditions involving the disturbance of biochemical equilibria (e.g. the skin disease psoriasis and β-fibrilloses). In these cases the NMR method is more elucidative than vibrational spectroscopy. However, owing to the fact that multiple spectral scans must be performed, it is very time consuming. It therefore appears that high resolution Fourier transform infra-red spectroscopy is a complementary method, but not as informative regarding structural details in secondary structures. Combining both methods together provides a powerful tool for structure analysis. 相似文献
202.
The formulae for conditional probabilities are derived with the term of NMR triad tacticities for the polymers whose polymerization process is described by an asymmetric Markovian process. The formulae obtained are applied to the polypropylene polymerized by Ziegler-Natta catalysis with external alkoxysilane donors. For both, unfractionated samples and heptane-insoluble fractions, four evidences are clarified as follows: Don the transformation from symmetric to (fluctuating) asymmetric sites the transformation of one (hereafter, L) site is much more enhanced than that of the other (D) site, 2) monotonous increase of isotacticity with an increase of the concentration of the donor is due to the increase of pLL, 3) aromatic donors are more effective than aliphatic ones for the improvement of isotacticity, and 4) the improvement of isotacticity after an addition of alkoxysilane is not due to the contribution from both of L and D sites, but the competition between the larger positive contribution from the former and the smaller negative one from the latter. 相似文献
203.
Teppo Martikainen Jukka PerttunenPaavo Yli-Olli A. Gunasekaran 《European Journal of Operational Research》1996
The purpose of this note is to analyze the effects of infrequent trading on the APT systematic risk components using Finnish data. Infrequent trading is reported to influence especially the first systematic risk component produced by factor analysis on stock returns. 相似文献
204.
Jukka Tuomela 《BIT Numerical Mathematics》1995,35(3):394-405
We construct in two ways stable schemes of arbitrarily high order for one dimensional wave equation. In both cases the stability limit is independent of the order. The other construction yields also automatically stable schemes for the heterogeneous case. In this case the estimated stability limit decreases slightly with order. 相似文献
205.
Yrjö Hiltunen Jukka Jokisaari Anja Pulkkinen Taito Väänänen 《Chemical physics letters》1984,109(5):509-513
The structure of benzene dissolved in various thermotropic nematic liquid crystals has been studied. 13C-methane was used as an internal “deformation reference”. The results indicate that the HH distance ratios obtained front the direct dipole-dipole coupling constants correspond to the hexagon values in cases where benzene is dissolved in mixtures of nematic liquid crystals which produce negligible dipolar CH splittings for methane. The ratio rCH/r CC for benzene is in good accord with the value obtained by other spectroscopic means. The proton structure of benzene in the smectic and nematic phases of p,p′-di-n-heptylazoxybenzene (HAB), however, does not follow the general trend observed in the purely nematic phases. But the dipolar CH splitting of methane also behaves inconsistently. 相似文献
206.
Harry G. Brittain Parviz Ansari Jukka Toivonen Lauri Niinisto Leon Tsao Dale L. Perry 《Journal of solid state chemistry》1985,59(2):259-264
The photoluminescence spectra of hydrated and anhydrous uranyl sulfates have been studied under conditions of high resolution at cryogenic temperatures. All uranyl sulfate systems were found to yield nonequivalent spectra: the energies for the electronic and vibronic origins were found to vary with the system, and certain uranyl vibrational frequencies exhibited a dependence on environment. These differences must reflect the various ways in which the uranyl centers are linked by the bridging sulfate groups, as this linking is the main difference between the various structures. 相似文献
207.
Heikkonen J Juujarvi J Ridderstad M Kotiaho T Ketola RA Tarkiainen V 《European journal of mass spectrometry (Chichester, England)》2004,10(5):573-578
This paper proposes a new maximum likelihood approach for the deconvolution of identity and quantity of individual compounds based on the multicomponent mass spectra measured by mass spectrometry (MS). Mixture analysis of multicomponent mass spectra is, typically, based on a linear multicomponent mass spectrum model, where the compounds of the measured spectra to be solved are explicitly stated and assumed to be known. In many cases, however, the measured spectrum may contain unknown compounds that are not explicitly stated in the model and a commonly used least square (LS) solution fails. Moreover, a standard improvement over the LS method in these cases, namely the M-estimation (ME) approach, also suffers from this same problem. Our method overcomes the limitations of the LS and ME methods by modeling the effect of the unknown compound(s) to the residual of the linear model. The experimental results presented show that this new approach can separate more robustly the complex multicomponent mass spectra into their individual constituents compared to the LS and ME methods. 相似文献
208.
Jukka T. Tanskanen Mikko Linnolahti Antti J. Karttunen Tapani A. Pakkanen 《Chemical physics》2007,340(1-3):120-126
The structural and electronic characteristics of fully hydrogenated armchair and zigzag carbon nanotubes have been determined by quantum chemical methods. With use of line group symmetries, the structures of nanotubes up to 10 nm in diameter could be optimized by periodic B3LYP calculations. “In–out” isomerism is shown to significantly stabilize perhydrogenated carbon nanotubes, the energetically most favorable structures being those with 1/3–1/2 of the carbon atoms endo-hydrogenated. In favored nanotubes the ratio of endo- to exo-hydrogens is 1:1, the stabilities increasing as a function of the diameter of the nanotube. The calculated band gaps indicate that the perhydrogenated carbon nanotubes are insulators. 相似文献
209.
In this paper, the novel application of time-of-flight secondary ion mass spectrometry (TOF-SIMS) for qualitative and semi-quantitative investigation of the surface chemistry of separation media based on beaded agarose is reported. Five different media were studied: DEAE Sepharose Fast Flow, Q Sepharose Fast Flow, SP Sepharose Fast Flow, Phenyl Sepharose Fast Flow at ligand densities between 7 and 33% (w/w) and the base matrix Sepharose 6 Fast Flow. The obtained TOF-SIMS spectra reveal significant chemical information regarding the ligands (DEAE, Q, SP and Phenyl) which are covalently attached to the agarose-based matrix Sepharose 6 Fast Flow. For the anion-exchange media (DEAE and Q Sepharose Fast Flow), the positive TOF-SIMS spectra yielded several strong characteristic fragment peaks from the amine ligands. Structural information was obtained, e.g. from the peak at m/z 173.20, originating from the ion structure [(C2H5)2NCH2CH2NH(C2H5)2l+, which shows that the ligand in DEAE Sepharose Fast Flow is composed of both tertiary and quaternary amines. The positive spectrum of Phenyl Sepharose Fast Flow contained major fragments both from the base matrix and the ligand. The cation-exchanger (SP Sepharose Fast Flow) gave rise to a positive spectrum resembling that of the base matrix (Sepharose 6 Fast Flow) but with a different intensity pattern of the matrix fragments. In addition, peaks with low intensity at m/z 109.94, 125.94 and 139.95 corresponding to Na2SO2+, Na2SO3+ and Na2SO3CH2+, respectively, were observed. The positive TOF-SIMS spectrum of Sepharose 6 Fast Flow contains a large number of fragments in the mass range up to m/z 200 identified as CxHyOz and CxHy structures. The results clearly show that positive TOF-SIMS spectra of different media based on Sepharose 6 Fast Flow are strongly influenced by the ligand coupled to the matrix. The negative TOF-SIMS spectra contained several ligand-specific, characteristic peaks for the cation-exchanger, having sulphonate as the ion-exchange group. Negative fragments such as S-, SO-, SO2-, SO3-, C2H3SO3-, C3H5SO3- and OC3H5SO3- were observed. Phenyl Sepharose Fast Flow, which has an uncharged group (Phenyl) coupled to the agarose matrix yielded one ligand-related peak corresponding to the C6H5O- fragment. DEAE and Q ligands could only be identified by the appearance of the fragments CN- and CNO- in the negative spectrum. However, a strong peak corresponding to the counter ion (Cl-) was observed. TOF-SIMS analysis can also be used for the investigation of residues from the coupling procedure that bonds the ligands to the matrix. One example is the observation of bromine peaks in the negative spectrum of Q Sepharose Fast Flow. Furthermore, it has also been shown that different ligand concentrations of Phenyl Sepharose Fast Flow can easily be detected by TOF-SIMS analysis. Information regarding the difference between the ligand density on the surface of the beads and in the bulk can also be obtained. However, spectra registered on the outermost surface and on the pore surface (crushed beads) of DEAE Sepharose Fast Flow clearly show that the agarose and the DEAE groups are homogeneously distributed in the beads. 相似文献
210.
The major route to convert lactic acid to high-molecular-weight polymers is ring-opening polymerization of lactide. We have investigated alternative synthesis routes based on oligomerization and chain linking to produce high-molecular-weight thermoplastic degradable polymers cost-effectively. Chain linking also offers new possibilities to prepare degradable polyesters for biomedical applications by extending the range of polymer properties achievable. In this paper, we briefly review different chain linking techniques used in our laboratory. Typically, lactic acid prepolymers with molecular weights of around 3,000-15,000 g x mol(-1) have been prepared by direct polycondensation. Hydroxyl terminated oligomers have been chain linked by using diisocyanate coupling agents, preferably 1,4-butane diisocyanate, forming poly(ester-urethanes). Poly(ester-amides) have been prepared by using 2,2'-bis(2-oxazoline) as coupling agent for carboxylic acid telechelic oligomers. Chain linking by end functionalization has been used in the preparation of poly(ester-anhydrides). In addition, a variety of crosslinked degradable polymers and copolymers have been synthesized through different crosslinking routes, by using methacrylic, itaconic or maleic double bonds or triethoxysilane moieties. A biodegradation test and ecotoxicological evaluation of the degradation products were carried out in addition to hydrolysis tests. Lactic acid based chain linked polymers were biodegradable and the degradation products were harmless. In hydrolysis tests, enzymatic degradation was pronounced in the chain linked poly(epsilon-caprolactone). 相似文献