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21.
D.B. Naik G.R. Dey A.D. Belapurkar K. Kishore 《Research on Chemical Intermediates》2004,30(6):594-603
Reactions of e
aq
–
, H atom and OH radicals with 4-pyridinemethanol (4-PM) and 4-pyridinecarboxaldehyde (4-PCA) have been studied at various pH values using the pulse radiolysis technique. Reaction of e
aq
–
with 4-PM and 4-PCA leads to the formation of pyridinyl and ketyl radicals of 4-PM and 4-PCA, respectively. Ketyl radicals formed from 4-PCA react with the parent molecule to give a dimeric radical species. At pH 7, the equilibrium constant for the dimer formation was determined to be 13 500 M-1. At pH 13 also dimer radical formation was observed. Reaction of e
aq
–
with 4-PM was found to give highly reducing pyridinyl radicals. Reaction of OH radicals with 4-PM gives a mixture of species,viz., OH adducts and radicals formed by H-atom abstraction from the –CH2OH moiety. Radicals formed by H-atom abstraction reaction from 4-PM were found to be reducing in nature. O– radicals were found to react with 4-PM exclusively by H-abstraction pathway. 相似文献
22.
The interaction of 2,2,2-trifluoroethanol (TFE) with concanavalin A has been investigated by using a combination of differential scanning calorimetry, isothermal titration calorimetry (ITC), circular dichroism (CD), and fluorescence spectroscopy at pH 2.5 and 5.2. All of the calorimetric transitions at both the pH values were found to be irreversible. In the presence of 4 mol kg(-1) TFE at pH 2.5, concanavalin A is observed to be in a partially folded state with significant loss of native tertiary structure. The loss of specific side chain interactions in the transition from native to the TFE-induced partially folded state is demonstrated by the loss of cooperative thermal transition and reduction of the CD bands in the aromatic region. Acrylamide quenching, 8-anilinonaphthalene sulfonate (ANS) binding, and energy transfer also suggest that in the presence of 4 mol kg(-1) TFE at pH 2.5 concanavalin A is in a molten globule state. ITC has been used for the first time to characterize the energetics of ANS binding to the molten globule state. ITC results indicate that the binding of ANS to the molten globule state and acid-induced state at pH 2.5 displays heterogeneity with two classes of non-interacting binding sites. The results provide insights into the role of hydrophobic and electrostatic interactions in the binding of ANS to concanavalin A. The results also demonstrate that ITC can be used to characterize the partially folded states of the protein both qualitatively and quantitatively. 相似文献
23.
Résumé Un grand nombre d'échantillons biologiques marins, s'étendant du varech au thon, à l'espadon et aux mammifères marins, ont
été analysés pour évaluer la teneur en mercure, sélénium et zinc grace à l'analyse par activation aux neutrons thermiques
et en employant un spectromètre Ge(Li). Dans ces conditions, des teneurs aussi faibles que 0,01 ppm de Hg, 0,02 ppm de Se,
et 0,2 ppm de Zn sont détectées. De nombreux résultats intéressants ont été obtenus et sont décrits. On est en train d'étendre
cette étude à d'autres éléments à l'état de trace en utilisant des séparations radio-chimiques après irradiation.
相似文献
24.
Gupta Madan Mohan Srivastava Alpana Tripathi Arvind Kumar Misra Himanshu Verma Ram Kishore 《平面色谱法杂志一现代薄层色谱法》2006,19(4):282-287
JPC – Journal of Planar Chromatography – Modern TLC - High-performance thin-layer chromatography (HPTLC) has been used for normal-phase separation of the components of hexane,... 相似文献
25.
Kaushik Chanda Milan Ch. Dutta Enamul Karim Jai N. Vishwakarma 《Journal of heterocyclic chemistry》2004,41(4):627-631
1‐(Aralkyl/aryl)‐3‐(alkyyaralkyl)‐5‐aroyl‐1,2,3,4‐tetrahydropyrimidines ( 2a‐c ) have been synthesized by dethiomethylation of 5‐aroyl‐6‐methylthio‐1,2,3,4‐tetrahydropyrimidines ( 1a‐c ). An alternative one‐pot synthetic strategy has been developed for the title compounds 2a‐t by the reaction of enaminones 3 with pri mary amine and formaldehyde in refluxing methanol in good yields. 相似文献
26.
Partial molar volumes for a homologous series of amino acids and peptides have been measured in aqueous 1M sodium acetate, sodium thiocyanate, and sodium sulfate at 25°C. These data have been utilized in conjunction with the data in water to deduce partial molar volumes of transfer V
2,m
0(tr) from water to these aqueous salt solutions. The volumes of transfer for the amino acids and peptides are found to be positive. The interpretation is that this result arises from the dominant interaction of the sodium salts with the charged centers of amino acids and peptides. Thermal denaturation of the structurally homologous proteins lysozyme and -lactalbumin has been studied in the presence of these salts. Significant thermal stabilization of hen egg-white lysozyme has been observed in the presence of sodium acetate and sodium sulfate. However, the thermal stabilization observed for -lactalbumin is very small in the presence of these salts and sodium thiocyanate leads to a lowering of its thermal denaturation temperature. The rise in the surface tension of aqueous salt solutions with salt concentration has been correlated with the calorimetric and volumetric measurements. The results show that V
2,m
0(tr) depends less on the type of electrolyte than on the ionic strength of the solution. The V
2,m
0(tr) values correlate very well with the increase in the surface tension of aqueous salt solutions, indicating significant role of surface tension in interactions of amino acids, peptides, or protein with the salts. 相似文献
27.
Reactions of OH radicals and some one-electron oxidants with 2-aminopyridine (2-AmPy) and 3-aminopyridine (3-AmPy) were studied in aqueous solutions using pulse radiolysis technique. The OH adduct of 2-AmPy at pH 9 has an absorption maximum at 360 nm along with a weak absorption band in the visible region and was found to be reactive with oxygen. The rate constant for its reaction with O2 was determined to be 1.0×108 dm3 mol−1 s−1. At pH 4 also, the OH adduct of 2-AmPy has an absorption band at 360 nm. However, there are differences in the absorption at other wavelengths. From the plot of ΔOD vs. pH at 340 nm, the pKa of the OH adduct was determined to be 6.5. Among the specific oxidants, only SO4−√ radicals were able to oxidize 2-AmPy. In the case of 3-aminopyridine (3-AmPy), the transient species formed by OH radical reaction at pH 9 has an absorption maximum at 410 nm with shoulder bands on both the sides. Its absorption spectrum at pH 4 was different indicating the existence of a pK value for the OH adduct. pKa of 3-AmPy-OH radical adduct species was evaluated to be 5.7. This adduct species was also found to be reactive with oxygen (k=7.6×106 dm3 mol−1 s−1). Specific one-electron oxidants like N3√, Br2−√ C2−√ and SO4−√ were able to oxidize 3-AmPy indicating that it is easier to oxidize 3-AmPy as compared to 2-AmPy. 相似文献
28.
The one-electron oxidation of toluidine blue by specific oxidising radicals such as Cl
2
−
, Tl(II), N3, Br
2
−
etc. has been studied by employing the pulse radiolysis technique. The Br
2
−
radical was found to be less efficient in oxidising toluidine blue as compared to Cl
2
−
., Tl+2 and N3. The semioxidised species exhibited only onepK
a indicating the presence of two conjugate acid-base forms whose spectral and kinetic features were evaluated. Reaction of
OH radicals with the dye gave rise to a transient species which exhibited spectral and kinetic features different from that
of the semioxidised species indicating that the mode of reaction of OH is different. 相似文献
29.
Highly Efficient One‐Pot Preparation of 1,2,4‐Oxadiazoles in the Presence of Diazabicycloundecene
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New highly efficient method for the cyclization of acylamidoximes in the presence of diazabicycloundecene was developed and incorporated into a general and practical one‐pot synthesis of 1,2,4‐oxadiazoles (11 examples, 85–97% yields). 相似文献
30.
It has been observed that poly(styrene peroxide) with a high molecular weight is thermally less stable than the same polymer with a low molecular weight. This has been explained as being due to the strain on the O-O bond due to the greater polymer chain length. 相似文献