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11.
Yohannes G Wiedmer SK Tuominen EK Kinnunen PK Riekkola ML 《Analytical and bioanalytical chemistry》2004,380(5-6):757-766
Lipid membranes are well recognized ligands that bind peripheral and integral proteins in a specific manner and regulate their function. Cytochrome c (cyt c) is one of the partner peripheral protein that binds to the lipid membranes via electrostatic and hydrophobic interactions. In this study, asymmetrical flow field-flow fractionation (AsFlFFF) was used to compare the interactions of cyt c with the acidic phospholipid 1,2-dimyristoyl-sn-glycero-3-phospho-rac-glycerol (DMPG), oleic acid (OA), and sodium dodecyl sulfate (SDS). The influence of pH and the cyt c–lipid molar mass ratios were evaluated by monitoring the diffusion coefficients and particle diameter distributions obtained for the free and lipid-bound protein. The hydrodynamic particle diameter of cyt c (pI 10) was 4.1 nm at pH 11.4 and around 4.2 nm at pH 7.0 and 8.0. Standard molar mass marker proteins were used for calibration to obtain the molar masses of free cyt c and its complexes with lipids. AsFlFFF revealed the binding of cyt c to DMPG and to OA to be mainly electrostatic. In the absence of electrostatic interactions, minor complex formation occurred, possibly due to the extended lipid anchorage involving the hydrophobic cavity of cyt c and the hydrocarbon chains of DMPG or SDS. The possibility of the formation of the molten globule state of cyt c, induced by the interaction between cyt c and lipids, is discussed.Electronic Supplementary Material Supplementary material is available for this article at 相似文献
12.
Pirita Rämänen Paavo A. Penttilä Kirsi Svedström Sirkka Liisa Maunu Ritva Serimaa 《Cellulose (London, England)》2012,19(3):901-912
Cellulose whiskers were prepared from wood- and cotton-based microcrystalline cellulose and dried by two methods: freeze-drying
or air-drying. The effect of drying method on the properties and structure of the whiskers were studied. Furthermore, the
influence of the source of cellulose on the nanoscale structure was investigated. Drying method was observed to slightly influence
the thermal stability of cellulose whiskers, whereas the char residue varied significantly depending on the drying process
performed. Small- and wide-angle X-ray scattering and solid state nuclear magnetic resonance spectroscopy were used to examine
the crystallinity and nanoscale structure of the dried whiskers. It was observed that the crystal structure and crystallinity
of cellulose whiskers remained during all treatments, whereas their nanoscale structure was significantly influenced by drying
method, neutralization, and source of cellulose. Relationships between thermal behavior and nanoscale structure were reported
and discussed. 相似文献
13.
Nikolaos Pahimanolis Arto Salminen Paavo A. Penttilä Juuso T. Korhonen Leena-Sisko Johansson Janne Ruokolainen Ritva Serimaa Jukka Seppälä 《Cellulose (London, England)》2013,20(3):1459-1468
In this paper, nanofibrillated cellulose/carboxymethyl cellulose (CMC) composite films were prepared using tape casting. The obtained transparent films showed shear induced partial alignment of fibrils along the casting direction, resulting in birefringence in cross polarized light. The carboxyl groups of CMC could be further utilized to create ionic crosslinking by treatment with glycidyl trimethyl ammonium chloride (GTMA). The GTMA treated composite films had improved mechanical properties both in wet and dry state. The chemical composition and morphologies of composites were analyzed with X-ray photoelectron spectroscopy, elemental analysis, scanning electron microscopy and wide-angle X-ray scattering. 相似文献
14.
Temporins are short (10–13 amino acids) and linear antimicrobial peptides first isolated from the skin of the European red
frog, Rana temporaria, and are effective against Gram-positive bacteria and Candida albicans. Similarly to other antimicrobial peptides, the association of temporins to lipid membranes has been concluded to underlie
their antimicrobial effects. Accordingly, a detailed understanding of their interactions with phospholipids is needed. We
conjugated a fluorophore (Texas Red) to a Cys containing derivative of temporin B (temB) and investigated its binding to liposomes
by fluorescence spectroscopy. Circular dichroic spectra for the Cys-mutant recorded in the absence and in the presence of
phospholipids were essentially similar to those for temB. A blue shift in the emission spectra and diminished quenching by
ferrocyanide (FCN) of Texas Red labeled temporin B (TRC-temB) were seen in the presence of liposomes. Both of these changes
can be attributed to the insertion of the Texas Red into the hydrophobic region of the bilayer. Resonance energy transfer,
steady state anisotropy, and fluorescence lifetimes further demonstrate the interaction of TRC-temB with liposomes to be enhanced
by negatively charged phospholipids. Instead, cholesterol attenuates the association of TRC-temB with membranes. The interactions
between TRC-temB and liposomes of varying negative surface charge are driven by electrostatics as well as hydrophobicity.
Similarly to native temporin B also TRC-temB forms amyloid type fibers in the presence of negatively charged liposomes. This
property is likely to relate to the cytotoxic activity of this peptide. 相似文献
15.
Sakari Leino Patrick JC May Paavo Alku Lassi A Liikkanen Hannu Tiitinen 《BMC neuroscience》2007,8(1):78
Background
In the field of auditory neuroscience, much research has focused on the neural processes underlying human sound localization. A recent magnetoencephalography (MEG) study investigated localization-related brain activity by measuring the N1m event-related response originating in the auditory cortex. It was found that the dynamic range of the right-hemispheric N1m response, defined as the mean difference in response magnitude between contralateral and ipsilateral stimulation, reflects cortical activity related to the discrimination of horizontal sound direction. Interestingly, the results also suggested that the presence of realistic spectral information within horizontally located spatial sounds resulted in a larger right-hemispheric N1m dynamic range. Spectral cues being predominant at high frequencies, the present study further investigated the issue by removing frequencies from the spatial stimuli with low-pass filtering. This resulted in a stepwise elimination of direction-specific spectral information. Interaural time and level differences were kept constant. The original, unfiltered stimuli were broadband noise signals presented from five frontal horizontal directions and binaurally recorded for eight human subjects with miniature microphones placed in each subject's ear canals. Stimuli were presented to the subjects during MEG registration and in a behavioral listening experiment. 相似文献16.
In this paper we introduce a storage process with singular continuous input. The input process is defined as the local time of a stationary reflecting Brownian motion with drift. Many basic charateristics of the process are computed explicitly, e.g., stationary distribution, distributions of the starting and ending time of on-going busy and idle periods. We also consider the multifractal spectrum of the input process and observe that it is independent of system parameters. 相似文献
17.
Paavo Salminen 《Probability Theory and Related Fields》1990,85(1):43-56
Summary In this note stochastic calculus is used to characterise multiplicative excessive functions of a binary branching Brownian motion with a constant creation rate. Some properties of the martingales given by invariant functions are studied. In particular, it is seen that these positive and unbounded martingales tend a.s. to 0 and are not square integrable. Informally speaking, they exhibit a clustering phenomenon in the underlying supercritical branching Brownian motion.This work was done while the author was visiting the University of British Columbia, Mathematical Department, and was partly supported by a NSERC grant. AMS 1980 subject classifications: primary 60J80, 60J65 secondary 60J60 相似文献
18.
Pekka V?h?oja Ilkka V?lim?ki Katri Heino Paavo Per?m?ki Toivo Kuokkanen 《Analytical sciences》2005,21(11):1365-1369
Certain wear metals (Fe, Cr, Ni, Cu and Zn) of various lubrication oils were determined by means of ICP-OES and FAAS. The kerosene dilution method, which is used widely together with ICP-OES, was applied with both methods here. Calibration standards were made from a commercial organo-metallic standard. Our aim was to clarify the possibility of using the quick kerosene dilution method together with FAAS for a rapid check for certain indicator metals. Metal determinations with FAAS were accurate enough for quantitative work in machine condition diagnostics and waste oil characterization, when compared with those with ICP-OES. 相似文献
19.
Pyropheophytin a, which is an unsymmetric porphyrin, has been titrated with trifluoroacetic acid (TFA) in tetrahydrofuran, the protonation reaction being followed by 13C NMR spectroscopy. TFA was added in small increments to a 0.28 M solution of pyropheophytin a in tetrahydrofuran, and the chemical shift changes of the macrocyclic carbons were determined as a function of the TFA increments. On the addition of TFA the signals of the α-carbons of ring II experienced a large upfield change, whereas the signals of all other macrocyclic carbons moved only slightly downfield or remained constant. These observations were interpreted as indicating the formation of a monocation in which the proton is attached to the nitrogen of ring II. The 13C protonation shifts of pyropheophytin a were compared with those previously reported for symmetric porphyrins. On the basis of this comparison, the basicity of the macrocyclic nitrogen atoms, the N–H tautomerism and the electron delocalization in structurally different porphyrin macrocycles are discussed. 相似文献
20.
The 13C NMR spectra of C-10 epimeric chlorophylls a and a′, pheophytins a and a′, pyrochlorophyll a and pyropheophytin a have been recorded and assigned by chemical shift comparison, by long-range selective 1H decoupling experiments and by the examination of the fully coupled spectra. Various factors influencing the 13C chemical shifts of the chlorophyll derivatives, e.g. the coordination of magnesium to the chlorin nucleus, the effect of solvent and the steric strain at the periphery of the macrocycle, have been examined. The 13C NMR spectra of chlorophyll a measured in acetone-d6 and tetrahydrofuran-d8 (THF) were compared, and remarkable solvent effects on the 13C chemical shifts were observed. These effects were interpreted mostly in terms of specific chlorophyll-solvent interactions. Different electron donor and steric properties of acetone and THF were considered to cause conformational alterations in the macrocycle, induced by the ligation of the solvent molecule(s) to the axial position(s) of the central magnesium atom of chlorophyll a. These results show that 13C NMR spectroscopy is a method of high information value for investigations of the unique electron donor acceptor (EDA) properties of the chlorophylls. The structural differences between the C-10 epimeric chlorophylls and pheophytins were examined in terms of the substituent chemical shift (SCS) parameters for the C-10 methoxycarbonyl group. The analysis showed that the change from the (10R) to the 10(S) configuration induces conformational alterations in the whole macrocycle which are, however, most prominent in rings IV and V. Owing to the increased steric interaction (repulsion) between the bulky substituents at C-7 and C-10, the peripheral strain is larger in the (10S) form, and is relieved by more pronounced deviations of rings IV and V from the macrocyclic plane compared with the (10R) form. The examination of the SCS parameters also showed that the peripheral steric strain is dissipated to a larger extent over the entire macrocycle in the Mg-free derivatives. These results confirm the previous conclusions based on 1H NMR and CD data. The possible function of chlorophyll a′ in photosynthesis is briefly discussed. 相似文献