The thermal denaturation process of bovine and human
both fatty acid containing and fatty acid free albumins in aqueous solution
was studied by use of differential scanning calorimetry. Human serum albumins
were found to be more stable than their bovine counterparts. Fatty acid free
albumins were characterized as generally less stable, more susceptible to
aggregation, their unfolding endothermic transition was less cooperative and
with the smaller degree of reversibility. Deconvolution analysis with using
a non-two-state model with two component transitions showed essential differences
in the thermodynamic parameters between all studied albumins, particularly
regarding the high-temperature component transition. 相似文献
The complexes of glyoxal (Gly), methylglyoxal (MGly), and diacetyl (DAc) with water have been studied using Fourier transform infrared (FTIR) matrix isolation spectroscopy and MP2 calculations with 6-311++G(2d,2p) basis set. The analysis of the experimental spectra of the Gly(MGly,DAc)/H2O/Ar matrixes indicates formation of one Gly...H2O complex, three MGly...H2O complexes, and two DAc...H2O ones. All the complexes are stabilized by the O-H...O(C) hydrogen bond between the water molecule and carbonyl oxygen as evidenced by the strong perturbation of the O-H, C=O stretching vibrations. The blue shift of the CH stretching vibration in the Gly...H2O complex and in two MGly...H2O ones suggests that these complexes are additionally stabilized by the improper C-H...O(H2) hydrogen bonding. The theoretical calculations confirm the experimental findings. They evidence the stability of three hydrogen-bonded Gly...H2O and DAc...H2O complexes and six MGly...H2O ones stabilized by the O-H...O(C) hydrogen bond. The calculated vibrational frequencies and geometrical parameters indicate that one DAc..H2O complexes, two Gly...H2O, and three MGly...H2O ones are additionally stabilized by the improper hydrogen bonding between the C-H group and water oxygen. The comparison of the theoretical frequencies with the experimental ones allowed us to attribute the calculated structures to the complexes present in the matrixes. 相似文献
Irradiation of chromium(III) complexes with oxalate and pyridinedicarboxylate ligands (pda = 2,3-, 2,4-, or 2,5-dicarboxylate) leads to diverse behaviors, dictated by light energy, presence of oxygen and the ligand nature. Irradiation within the MC bands is unaffected by O2 and results in ligand substitution. The LMCT excitation is effective only when oxalate is coordinated to Cr(III); then electron transfer from oxalate to central ion generates an intermediate, consisted of a Cr(II)species and the C2O4? radicals. The species undergo fast redox reactions dependent on the presence of O2 and the pda ligand.(1) In anoxic medium the fast outersphere electron transfer from Cr(II) to solvent, generates hydrated electrons and re-oxidizes the chromium centre to CrIII. Then geminate recombination regenerates substrate, whereas competitive release of the C2O4? radical leads to substitution of one oxalate ligand by two water molecules (aquation induced by the LMCT excitation). In the presence of the pda ligand the outersphere electron transfer is accompanied by the innersphere CT, generating Cr(III) coordinated to two radical ligands: C2O4? and pda3?; the intermediate releases also eaq?, but this reaction is slower than that of the homoleptic oxalate complex. Hydrated electrons are scavenged also by the released radicals. All these processes are completed within microseconds and in consequence, the Cr(III) complexes irradiated in deoxygenated solutions are insensitive to subsequent oxygenation.(2) When UV-irradiation is carried out in oxygenated medium reaction of Cr(II) species with molecular oxygen competes with the outer- or inner electron transfer observed in anoxic medium. Both these pathways result in generation of chromate(VI). Quantum yield of the Cr(VI) production is sensitive to the presence and structure of pda ligand, decreasing within the series 2,3-pda > 2,4-pda > 2,5-pda. 相似文献
The aim of the paper is to point out some imprecision in Srivastava and Hui’s tests for multivariate normality. A correction for their tests is proposed. 相似文献
The influence of antiretroviral drug zidovudine treatment during pregnancy on mandible development in newborn rats was studied. The fluorescence of mandibles from 7-, 14-
and 28-days old individuals was measured by means of fiber-optical fluorescence analyzer with 407 nm laser excitation. Obtained
results revealed disturbing effect of maternal zidovudine administration on mandible fluorescence intensity which should decrease with bone development. Small changes in fluorescence
of porphyrin forms are maintaining in the first month of newborns life while the changes observed in 440–585 nm range disappear. 相似文献
We consider the classic spring–mass model of running which is built upon an inverted elastic pendulum. In a natural way, there arises an interesting boundary value problem for the governing system of two nonlinear ordinary differential equations. It requires us to choose the stiffness to ascertain that after a complete step, the spring returns to its equilibrium position. Motivated by numerical calculations and real data, we conduct a rigorous asymptotic analysis in terms of the Poicaré–Lindstedt series. The perturbation expansion is furnished by an interplay of two time scales what has an significant impact on the order of convergence. Further, we use these asymptotic estimates to prove that there exists a unique solution to the aforementioned boundary value problem and provide an approximation to the sought stiffness. Our results rigorously explain several observations made by other researchers concerning the dependence of stiffness on the initial angle of the stride and its velocity. The theory is illustrated with a number of numerical calculations.
A sequence of two reactions: the Petasis reaction, in which an aminoacetaldehyde acetal was used as the amine component, followed by Pomeranz–Fritsch–Bobbitt cyclization, has been shown to be a convenient and simple method for the synthesis of tetrahydroisoquinoline-1-carboxylic acids. Using this method several acids have been prepared in good to excellent yields and characterized as hydrochloride salts. 相似文献
Irreversible photooxidation based on N–O bond fragmentation is demonstrated for N‐methoxyheterocycles in both the singlet and triplet excited state manifolds. The energetic requirements for bond fragmentation are studied in detail. Bond fragmentation in the excited singlet manifold is possible for ππ* singlet states with energies significantly larger than the N–O bond dissociation energy of ca 55 kcal mol?1. For the nπ* triplet states, N–O bond fragmentation does not occur in the excited state for orbital overlap and energetic reasons. Irreversible photooxidation occurs in the singlet states by bond fragmentation followed by electron transfer. Irreversible photooxidation occurs in the triplet states via bimolecular electron transfer to the donor followed by bond fragmentation. Using these two sensitization schemes, donors can be irreversibly oxidized with oxidation potentials ranging from ca 1.6–2.2 V vs SCE. The corresponding N‐ethylheterocycles are characterized as conventional reversible photooxidants in their triplet states. The utility of these sensitizers is demonstrated by irreversibly generating the guanosine radical cation in buffered aqueous solution. 相似文献