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941.
We have developed a sequence-specific model for predicting slopes (S) in the fundamental equation of linear solvent strength theory for the reversed-phase HPLC separation of tryptic peptides detected in a typical bottom-up-proteomics experiment. These slopes control the variation in the separation selectivity observed when the physical parameters of chromatographic separation, such as gradient slope, flow rate, and column size are altered. For example, with the use of an arbitrarily chosen set of tryptic peptides with a 4-times difference in the gradient slope between two experiments, the R(2)-value of correlation between the observed retention times of identical species decreases to ~0.993-0.996 (compared to a theoretical value of ~1.00). The observed retention time shifts associated with variations of the gradient slope can be predicted a priori using the approach described here. The proposed model is based on our findings for a set of synthetic species (Vu, H.; Spicer, V.; Gotfrid, A.; Krokhin, O. V. J. Chromatogr., A, 2010, 1217, 489-497), which postulate that slopes S can be predicted taking into account simultaneously peptide length, charge, and hydrophobicity. Here we extend this approach using an extensive set of real tryptic peptides. We developed the procedure to accurately measure S-values in nano-RP HPLC MS experiments and introduced sequence-specific corrections for a more accurate prediction of the slopes S. A correlation of ~0.95 R(2)-value between the predicted and experimental S-values was demonstrated. Predicting S-values and calculating the expected retention time shifts when the physical parameters of separation like gradient slope are altered will facilitate a more accurate application of peptide retention prediction protocols, aid in the transfer of scheduled MRM (SRM) procedures between LC systems, and increase the efficiency of interlaboratory data collection and comparison. 相似文献
942.
943.
Aerosols are considered major players in climate change and represent health hazards. Dicarboxylic acids are among a major class of components that form secondary organic atmospheric aerosols. To understand the atmospheric transformation of these compounds, kinetic studies on the ozonolysis and the photoinduced ozonolysis (lambda > or = 250 nm) of aqueous solutions of seven (C2-C9) dicarboxylic acids, which have been identified in atmospheric aerosols, were performed using Fourier transform infrared and ultraviolet-visible spectroscopy. The measured apparent rate constants for dicarboxylic acids in 0.1 mol L(-1) aqueous solutions at 298 +/- 2 K are as follows: oxalic, (2.7 +/- 0.1) x 10(-2); malonic, (5.5 +/- 0.1); succinic, (6.7 +/- 0.4) x 10(-4); glutaric, (1.3 +/- 0.2) x 10(-3); adipic, (1.7 +/- 0.1) x 10(-3); pimelic, (4.4 +/- 0.1) x 10(-3); and pinic, (2.5 +/- 0.1) x 10(-2) (L mol(-1) s(-1)). An empirical equation is provided to estimate the ozonolysis rate constant of dicarboxylic acids containing more than three carbon atoms for which no experimental data exists. A mechanism for malonic acid ozonolysis, which explains its fast ozonolysis rate constant, is also suggested. The implications of our results to atmospheric chemistry indicate that ozonolysis and photoinduced ozonolysis are not significant removal pathways for dicarboxylic acids. 相似文献
944.
Borisov OV Goshe MB Conrads TP Rakov VS Veenstra TD Smith RD 《Analytical chemistry》2002,74(10):2284-2292
The development of methods to chemically modify and isolate cysteinyl-residue-containing peptides (Cys-peptides) for LC-MS/MS analysis has generated considerable interest in the field of proteomics. Methods using isotope-coded affinity tags (ICAT) and (+)-biotinyl-iodoacetamidyl-3,6-dioxaoctanediamine (iodoacetyl-PEO-biotin) employ similar Cys-modifying reagents that contain a thiolate-specific biotin group to modify and isolate Cys-containing peptides in conjunction with immobilized avidin. For these strategies to be effective on a proteome-wide level, the presence of the ICAT or acetyl-PEO-biotin tag should not interfere with the efficiency of induced dissociation in MS/MS experiments or with the identification of the modified Cys-peptides by automated database searching algorithms. We have compared the collision-induced dissociation (CID) fragmentation patterns of peptides labeled with iodoacetyl-PEO-biotin and the ICAT reagent to those of the unmodified peptides. CID of Cys-peptides modified with either reagent resulted in the formation of ions attributed to the modified Cys-peptides as well as those unique to the labeling reagent. As demonstrated by analyzing acetyl-PEO-biotin labeled peptides from ribonuclease A and the ICAT-labeled proteome of Deinococcus radiodurans, the presence of these label-specific product ions provides a useful identifier to discern whether a peptide has been modified with the Cys-specific reagent, especially when a number of peptides analyzed using these methods do not contain a modified Cys residue, and to differentiate identical Cys-peptides labeled with either ICAT-d0 or ICAT-d8. 相似文献
945.
Michailovich O Adam D 《IEEE transactions on ultrasonics, ferroelectrics, and frequency control》2002,49(8):1060-1072
An approach to computing estimates of the ultrasound pulse spectrum from echo-ultrasound RF sequences, measured from biological tissues, is proposed. It is computed by a "projection" algorithm based on the Discrete Wavelet Transform (DWT) using averaging over a range of linear shifts. It is shown that the robust, shift invariant estimate of the ultrasound pulse power spectrum can be obtained by the projection of RF line log spectrum on an appropriately chosen subspace of L2(R) (i.e., the space of square-integrable functions) that is spanned by a redundant collection of compactly supported, scaling functions. This redundant set is formed from the traditional (in Wavelet analysis) orthogonal set of scaling functions and also by all its linear (discrete) shifts. A proof is given that the estimate, so obtained, could be viewed as the average of the orthogonal projections of the RF line log spectrum, computed for all significant linear shifts of the RF line log spectrum in frequency domain. It implies that the estimate is shift-invariant. A computationally efficient scheme is presented for calculating the estimate. Proof is given that the averaged, shift-invariant estimate can be obtained simply by a convolution with a kernel, which can be viewed as the discretized auto-correlation function of the scaling function, appropriate to the particular subspace being considered. It implies that the computational burden is at most O(n log2 n), where n is the problem size, making the estimate quite suitable for real-time processing. Because of the property of the wavelet transform to suppress polynomials of orders lower than the number of the vanishing moments of the wavelet used, the presented approach can be considered as a local polynomial fitting. This locality plays a crucial role in the performance of the algorithm, improving the robustness of the estimation. Moreover, it is shown that the "averaging" nature of the proposed estimation allows using (relatively) poorly regular wavelets (i.e., short filters), without affecting the estimation quality. The latter is of importance whenever the number of calculations is crucial. 相似文献
946.
Zhijian Shen Daniel Ashkin Oleg Babushkin Thommy Ekstrm 《Journal of the American Ceramic Society》1997,80(3):817-821
The formation of the melilite solid solution phase (M'), Sm2 Si3−x Alx O3+x N4−x , in an α-sialon sample of overall composition Sm0.6 Si9.28 Al2.69 O1.36 N14.76 , was studied as a function of time in the temperature interval 1375–1525°C. The alpha-sialon ceramic contained only minor amounts of the 21R sialon polytype and some residual grain-boundary glass before heat treatment. In situ studies by high-temperature X-ray diffraction were combined with postsintering heat treatment followed by quenching. The M'-phase was found to be formed by two different mechanisms: either crystallization of the residual grain-boundary liquid or a direct decomposition of the α-sialon phase. The liquid crystallized during the first 10–15 min of heat treatment, yielding a rapid M'-phase formation, and further formation of M'-phase continued at a much slower rate, related to the decomposition of α-sialon. 相似文献
947.
948.
Younis A Krifucks O Fleminger G Heller ED Gollop N Saran A Leitner G 《The Journal of dairy research》2005,72(2):188-194
The involvement of Staphylococcus aureus exosecretions in bovine udder infection (Younis et al. 2003) suggests that four different monomer protein bands appearing between 36 and 31 kDa, are associated with the severity of the cow's infection response. Three out of these four bands have been identified by means of protein sequencing. Band B, with a MW of 35 kDa was identified as Panton-Valentaine leucocidin LukF'-PV chain- Staph. aureus; band C, with a MW of 32 kDa was identified as leucocidin chain LukM precursor- Staph. aureus; and band D was found to be similar, but not identical, to phosphatidylinositol-specific phospholipase-C-X. Bands B and C were purified by gel filtration using FPLC. The ability of these proteins to induce udder inflammation in vivo, and proliferation response in vitro and cytokine secretion were tested for both the crude exosecretions and purified bands. Three cows were inoculated intracisternally, with three quarters receiving either 0.007-0.008 mg (as total proteins) of Staph. aureus FR2449/1 bacterial exosecretion, pooled fraction 39-41 (bands B and C), or culture broth medium. The fourth quarter was left free as a control. Quarters that received fraction 39-41 of Staph. aureus FR2449/1, exhibited induced inflammation, which was indicated by increased somatic cell count and enhanced NAGase activity that was significantly higher than that of the original Staph. aureus FR2449/1 bacterial exosecretion. Proliferation tests of bovine blood lymphocytes in vitro showed that the pooled fraction 39-41 stimulated bovine proliferation of mononuclear cells much more than the original Staph. aureus FR2449/1 bacterial exosecretion. Secretion of TNF-alpha, IL-1beta, IL-6 and IL-8 was in accordance with the contents of LukF'-PV and LukM precursor in the exosecretions. The results suggest that LukM/ LukF' induce inflammation into the udder by a mechanism similar to that of LPS or by a unique mechanism(s) which requires further investigation. 相似文献
949.
The X-ray pattern of a mass of very fine non-distinguishable anatomical structures alters completely from radiograph to radiograph due to the unavoidable movements of the patient during the exposure. The corresponding image component shows noise-like behaviour and is therefore referred to as the anatomical noise. Reducing this component would enhance the quality of the clinical X-ray image and increase the detectability of radiological signal. We have found that by comparing two X-ray images of the same anatomy acquired under slightly different imaging geometry, it is possible to reduce the anatomical noise in one of the image pair. The proposed method, which allows this, is based on the appropriate attenuation in the wavelet domain. The values of attenuating factors for the wavelet coefficients are proportional to the correlation between the corresponding features of both images. This method was tested for different changes in the imaging geometry. In the case of no geometrical changes, only the quantum and the electronic noise are reduced. An effect of de-noising for the investigated images is obvious. 相似文献
950.
Former studies by Hoeschen and Buhr indicated a higher total noise in a thorax image than expected from technical noise, i.e. quantum and detector noise. This difference results from the overlay of many small anatomical structures along the X-ray beam, which leads to a noise-like appearance without distinguishable structures in the projected image. A method is proposed to quantitatively determine this 'anatomical noise' component, which is not to be confused with the anatomical background (e.g. ribs). This specific anatomical noise pattern in a radiograph changes completely when the imaging geometry changes because different small anatomical structures contribute to the projected image. Therefore, two images are taken using slightly different exposure geometry, and a correlation analysis based on wavelet transforms allows to determining the uncorrelated noise components. Since the technical noise also differs from image to image, which makes it difficult to separate the anatomical noise, images of a lung phantom were produced on a low-sensitive industrial X-ray film using high-exposure levels. From these results, the anatomical noise level in real clinical thorax radiographs using realistic exposure levels is predicted using the general dose dependence described in the paper text and compared with the quantum and detector noise level of an indirect flat-panel detector system. For consistency testing, the same lung phantom was imaged with the same digital flat-panel detector and the total image noise including anatomical noise is determined. The results show that the relative portion of anatomical noise may exceed the technical noise level. Anatomical noise is an important contributor to the total image noise and, therefore, impedes the recognition of anatomical structures. 相似文献