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101.
We describe a useful method for the efficient ionization and relative quantification of peptides containing serine/threonine phosphorylation sites. This method is based on beta-elimination of the phosphate group from serine/threonine phosphorylation sites under alkaline conditions, followed by Michael addition reaction with N-(2-mercaptoethyl)-6-methylnicotinamide (MEMN). As a result of the derivatization reaction, the negatively charged phosphate group is substituted with the nicotinoyl moiety to improve the ionization efficiency of the derivatized peptide. The combination of d(3)-labeled MEMN (d(3)-MEMN) and MEMN (d(0)-MEMN) generates a 3 Da mass difference between d(3)-MEMN-labeled and d(0)-MEMN-labeled peptides, which is a useful signature for the identification of peptides containing serine/threonine phosphorylation sites in the matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrum. Moreover, the mass difference is useful for the quantitative analysis of serine/threonine phosphorylation in proteins. In this paper, we describe the synthesis of d(0)/d(3)-labeled MEMN and an application of our approach to model peptides and proteins.  相似文献   
102.
We describe a convenient and useful method for the identification and relative quantification of proteins using light and heavy reagents, 1-(6-methylnicotinoyloxy)succinimides (6-CH(3)-Nic-NHS and 6-CD(3)-Nic-NHS, respectively). This method is based on the chemical derivatization of amino groups of tryptic peptides with these reagents, i.e., the basic moiety of the reagents thus incorporated into both the N-terminal amino group and the epsilon-amino group of the lysine residue would improve the ionization efficiency of tryptic peptides. An increase in protein sequence coverage is achieved by derivatization with these reagents or by combination of mass values before and after derivatization. Since a combination of 6-CH(3)-Nic-NHS and d(3)-labeled reagent (6-CD(3)-Nic-NHS) generates a 3 Da mass difference per reaction site, the d(3)-labeled reagent shifts the mass values of d(0)-labeled peptides according to the number of reactive amino groups in the peptides. In the case of tryptic peptides, the mass values of C-terminal arginine and lysine peptides are shifted by 3 and 6 Da, respectively. Further, the 3 Da mass difference between 6-CH(3)-Nic-NHS and 6-CD(3)-Nic-NHS offers a means for the relative quantification of protein by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.  相似文献   
103.
Regioselective and high-yielding nuclear monobromination of aromatic ethers can be accomplished with a combination of NaClO2, NaBr, and Mn(acac)3 catalyst in dichloromethane under mild and neutral conditions with the aid of Montmorillonite K10.  相似文献   
104.
Ring A of nukacin ISK-1, which is also present in different type-A(II) lantibiotics, resembles a lipid II-binding motif (TxS/TxD/EC, x denotes undefined residues) similar to that present in mersacidin (type-B lantibiotics), which suggests that nukacin ISK-1 binds to lipid II as a docking molecule. Results from our experiments on peptidoglycan precursor (UDP-MurNAc-pp) accumulation and peptide antagonism assays clearly indicated that nukacin ISK-1 inhibits cell-wall biosynthesis, accumulating lipid II precursor inside the cell, and the peptide activity can be repressed by lipid I and lipid II. Interaction analysis of nukacin ISK-1 and different ring A variants with lipid II revealed that nukacin ISK-1 and nukacin D13E (a more active variant) have a high affinity (K(D) = 0.17 and 0.19 μM, respectively) for lipid II, whereas nukacin D13A (a less active variant) showed a lower affinity, and nukacin C14S (a negative variant lacking the ring A structure) exhibited no interaction. Therefore, on the basis of the structural similarity and positional significance of the amino acids in this region, we concluded that nukacin ISK-1 binds lipid II via its ring A region and may lead to the inhibition of cell-wall biosynthesis.  相似文献   
105.
Carbon monoxide reacts with iodine pentoxide at 42°C to produce iodine vapor, which is dtected by a solid-state electrochemical detector, essentially a Pt/AgI/Ag galvanic cell. The response begins to rise steeply 3.7 s after a 1.1-ml gas sample is introduce and reaches a maximum after a further 1.2 s. The response is linearly related to the concentration of carbon monoxide up to 2 ppm from the detection limit of 0.03 ppm. Interferences such as H2S and C2H4 are removed by 5A molecuarl sieve; H2 (1%), CH4 (5%) and C2H4 (5%) are without effect.  相似文献   
106.
Let (X Δ) be a four-dimensional log variety that is projective over the field of complex numbers. Assume that (X, Δ) is not Kawamata log terminal (klt) but divisorial log terminal (dlt). First we introduce the notion of “log quasi-numerically positive”, by relaxing that of “numerically positive”. Next we prove that, if the log canonical divisorK X+Δ is log quasi-numerically positive on (X, Δ) then it is semi-ample.  相似文献   
107.
2,7-Dimethylpyrrolo[1,2-a]quinoline (1) was synthesized from 2,6-dimethylquinoline and bromoaeetone via a Tsebitsehibabin reaction. The electrophilic substitution reactions of I, namely, nitrosation, acylation, diazonium coupling, formylation, bromination, and nitration were studied.  相似文献   
108.
109.
The ionic interaction of poly(ethylene-co-methacrylic acid) ionomer neutralized with Mn2+ or Cu2+ was studied by ESR spectroscopy to explore the local structure in the ionic aggregate. ESR spectra of the ethylene ionomer were obtained as functions of degree of neutralization and temperature. The existence of both isolated and aggregated cations in the ionomer was confirmed by ESR. In addition, the formation of a Cu2+?Cu2+ dimer structure similar to the crystal structure of copper acetate monohydrate was found in ethylene ionomer containing the Cu2+. Cation-cation interactions changed markedly around 70°C with increasing temperature, representing the onset of the motion of cations in the aggregated ionic structure.  相似文献   
110.
The analogues of 2-(E-n or Z-n-decenoylamino)ethyl carbamoylmethyl sulfide, including the modifications of sulfide portion, double bond in decenoyl chain and alkyl sulfide moiety, were synthesized and their inhibitory effects on stress-induced ulceration in rats were compared. Replacing the sulfura atom by methylene group or oxygen atom reduced the effect of potency. Saturation of the double bond in the decenoyl chain tended to reduce the anti-ulcerogenic activity in rats. There was no relationship between the position of double bond in decenoyl chain and the pharmacological activity. On the other hand, compounds with E-configuration showed stronger anti-ulcer activity than the corresponding Z-type of compounds. Among 9 kinds of S substituted alkyl groups for carbamoylmethyl, 2-(E-2-decenoylamino)ethyl 2-cyclohexylethyl sulfide showed the most potent anti-ulcerogenic activity in rats and also showed the lowest acute toxicity in mice.  相似文献   
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