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21.
A method for the preparation of insulin derivatives which have protected sulfhydryl group(s) at definite site(s) on the molecule is described. Porcine insulin reacts with S-acetylmercaptosuccinic anhydride to afford four species of insulin derivatives that have 2 (or 3)-acetylmercapto-3-carboxypropanoyl group(s) at i) Gly(A1), ii) Gly(A1) and Phe(B1), iii) Gly(A1) and Lys(B29), and iv) Gly(A1), Phe(B1) and Lys(B29) positions. The derivatives are efficiently separated in a preparative scale by anion-exchange high-performance liquid chromatography on a TSKgel DEAE-2SW column. The four derivatives are all readily deacetylated with hydroxylamine to give the corresponding sulfhydryl insulin derivatives. 相似文献
22.
Lin M Katsumura Y He H Muroya Y Han Z Miyazaki T Kudo H 《The journal of physical chemistry. A》2005,109(12):2847-2854
The spectral changes as well as the reaction kinetics of the transient species of 4,4'-bipyridyl (4,4'-bpy) have been experimentally investigated by pulse radiolysis techniques up to 400 degrees C. The results show that the transient species such as OH adduct 4,4'-bpyOH*, monoprotonated electron adduct 4,4'-bpyH*, and doubly protonated electron adduct 4,4'-bpyH2+* have 15-20 nm blue shifts from room temperature to 400 degrees C. For a deaerated neutral solution of 4,4'-bpy in the presence of tert-butyl alcohol, ethanol, or NaCOOH, the doubly protonated electron adduct is the main transient species at room temperature. But at temperatures > 350 degrees C, a monoprotonated form, the N-hydro radical 4,4'-bpyH*, becomes predominant. Interestingly, at room temperature, CO2-* could not efficiently react with 4,4'-bpy, but the reaction was accelerated with increasing temperature; at 350 degrees C, this reaction completed within 2 mus. Using an alkaline solution (pH = 11.5) of 4,4'-bpy in the presence of tert-butyl alcohol, we studied the N-hydro radical 4,4'-bpyH* from room temperature to 400 degrees C at 25 MPa. An estimation of the temperature-dependent G(e(aq)-) at 25 MPa agrees with our previous result with methyl viologen as a scavenger. 相似文献
23.
24.
Nakamura Y Asami A Ogawa T Inokuma S Nishimura J 《Journal of the American Chemical Society》2002,124(16):4329-4335
The reactions of [60]fullerene with bis-o-quinodimethane precursors 3, 4, and 5 containing a dibenzo-18-crown-6, 24-crown-8 and 30-crown-10 moiety, respectively, were investigated. Both 3 and 4 provided trans-4 bisadducts 6a and 7a, respectively, as major product, though the selectivity in the latter was lower than that in the former. As minor product, 6b (cis-2) was produced from 3, while 7c (e) as well as 7b (cis-2) were produced from 4. Precursor 5 exclusively afforded e bisadduct 8 without any other regioisomers. These bisadducts showed different ionophoric properties from one another; for instance, 6a and 7b exhibited a high complexing ability toward the K+ ion, while 6b hardly showed complexation with any alkali metal ions. The selectivity coefficients (K(Na,K)(pot)) of 6a and 7b toward K+ over Na+ ion, determined with an ion-selective electrode, were much higher than that of dibenzo-18-crown-6. 相似文献
25.
Oseki Y Fujitsuka M Hara M Cai X Ie Y Aso Y Majima T 《The journal of physical chemistry. B》2005,109(21):10695-10698
Photophysical properties of oligo(2,3-thienyleneethynylene)s (nTE, n denotes the number of thiophene rings, n = 2, 3) in benzene were investigated using steady-state, time-resolved fluorescence, and transient absorption spectroscopies. For 2TE, generation of the radiative S2 and nonradiative S1 states was confirmed. Upon excitation, the S2 state was initially generated and deactivated to the S1 state within 10 ps. The S1 state exhibited the transient absorption band at 470 nm, of which the lifetime was estimated to be 5.3 ns. In the case of 3TE, on the other hand, it was revealed that the radiative S1 state with a transient absorption peak at 650 nm was generated upon excitation. The T1 states of nTE were generated from the S1 states. The quantum yields were estimated to be 0.52 and 0.54 for 2TE and 3TE, respectively. Extremely fast reactions in the higher triplet excited state were indicated for both 2TE and 3TE. 相似文献
26.
Okada Y Yokozawa M Akiba M Oishi K O-kawa K Akeboshi T Kawamura Y Inokuma S Nakamura Y Nishimura J 《Organic & biomolecular chemistry》2003,1(14):2506-2511
A variety of aromatic compounds with both activating and deactivating substituents were brominated with sodium monobromoisocyanurate (SMBI) 1, diethyl ether, diethyl ether-methanesulfonic acid, trifluoroacetic acid, or sulfuric acid were employed as solvents. Thus nitrobenzene was conveniently brominated in sulfuric acid, benzene was readily monobrominated in diethyl ether-methanesulfonic acid, and phenol was selectively brominated at the ortho position under mild conditions in refluxing diethyl ether. With substituents that are easily protonated, trifluoroacetic acid may be employed as solvent in the reaction with 1, in contrast NBS was ineffective in trifluoroacetic acid. This renders 1 a superior reagent relative to NBS. In addition to aromatics, alkenes, ketones and esters were also brominated with 1. Diethyl malonate was brominated with 1 and then subjected to a Bingel reaction with NaH to afford the desired methanofullerene in reasonable yield. 相似文献
27.
28.
The fluorescence derivatization of nucleotides with 2-(5-chlorocarbonyl-2-oxazolyl)-5,6-methylenedioxybenzo++ furan in the presence of sodium azide and the separation of the derivatives by high-performance liquid chromatography are described. The reagent reacts with 5'-terminal hydroxyl groups of nucleotides to produce the corresponding fluorescent carbamates. The derivatives of mono- and oligonucleotides are separated by chromatography on a reversed phase column (TSKgel ODS-80TM) and the derivatives of octa- and deca-nucleotides on a size exclusion column (TSKgel G3000SWXL). The detection limits (signal-to-noise ratio = 3) are 0.8-6.0 pmol on column. 5'Phosphorylated nucleotide also gives a fluorescent derivative after alkaline phosphatase-mediated dephosphorylation. 相似文献
29.
A detection system based on on-line post-column fluorescence derivatization is described for the determination of N-terminal tyrosine-containing peptides by reversed-phase high-performance liquid chromatography. The peptides are automatically converted into fluorescent derivatives by reaction with hydroxylamine, cobalt (II) and borate after peptide separation on a reversed-phase column (TSKgel ODS-120T) followed by passage through an ultraviolet absorbance detector. The reaction system permits the fluorescence detection at 435 nm (emission) with excitation at 335 nm for N-terminal tyrosine-containing synthetic peptides in as little as picomole amounts. The facile fluorescence detection of N-terminal tyrosine-containing fragments produced from methionine-enkephalin by enzymatic degradation using a rat brain homogenate was achieved by comparison with the ultraviolet absorption detection at 215 nm. 相似文献
30.
In contrast to the previously reported short time required (1 h) for photolysis of 6-chloro-1,3-dimethyluracil (6-CIDMU) and mesitylene, in the presence of TFA, resulting in two major products: 1,3,6,8,10-pentamethylcyclooctapyrimidine derivative (1d), and diazapentacyclo[6.4.0.0(1,3).0(2,5).0(4,8)]dodecane (2c), prolonged irradiation (18h) of this same mixture yields novel pentalenopyrimidine derivatives, including diazapentacyclo[6.4.0.0(1,3).0(2,6).0(4,8)]dodecane (3c). 相似文献