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1.
S. F. Baranovskii P. A. Bolotin M. P. Evstigneev 《Journal of Applied Spectroscopy》2006,73(2):171-177
We have studied self-association of aromatic molecules of the thiazine dye methylene blue in aqueous solution, using a dimer
model. We have determined the dimerization equilibrium constant for the dye molecules KD = 3900 ± 800 M−1 at T = 293 K. We have decomposed the experimental spectrum into dimer and monomer components. Using the ratio of the molar
absorption coefficients for two absorption bands of the dimer spectrum, we obtained the “average” value of the angle between
the electronic transition moments of the molecules in the dimers, α = 48°.
We have studied heteroassociation of methylene blue (MB) and 1,3,7-trimethylxanthine (caffeine) molecules in aqueous solution.
We have calculated the heteroassociation constant as 200 ± 34 M−1. We conclude that heteroassociation of methylene blue and caffeine molecules leads to a lower effective dye concentration
in solution, which hypothetically may affect its biological activity.
We have determined the values of the Gibbs free energy, the enthalpy, and the entropy for dimerization of methylene blue molecules:
ΔG293 = −(20 ± 3) kJ/mol, ΔH = −(25 ± 9) kJ/mol, Δ S293 = −(17 ± 6) J/mol·K; and for methylene blue-caffeine heteroassociation: ΔG293 = −(13 ± 3) kJ/mol, ΔH = −(14 ± 10) kJ/mol, ΔS293 = −(2.4 ± 0.2) J/mol·K, respectively. We have shown that the methylene blue aggregates and the heteroassociates with caffeine
are predominantly stabilized by dispersion interactions between the chromophore molecules in the associates.
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 158–163, March–April, 2006. 相似文献
2.
S. F. Baranovsky P. A. Bolotin M. P. Evstigneev D. N. Chernyshev 《Journal of Applied Spectroscopy》2009,76(1):132-139
Two component (ethidium bromide–caffeine, ethidium bromide–DNA) and three component (ethidium bromide–caffeine–DNA) systems
in aqueous saline (0.01 M NaCl) phosphate buffer solutions (pH 6.86, T = 298 K) are studied spectrophotometrically. The equilibrium constants for dimerization of caffeine, K
D
= 1.22 ± 2 M−1, and for heteroassociation of ethidium bromide with caffeine, K = 71 ± 8 M−1, in ethidium bromide–caffeine systems are determined. When the concentration of caffeine is increased, the dynamic equilibrium
of the solution shifts toward formation of heterocomplexes which are, presumably, stabilized by dispersive and hydrophobic
interactions of chromophores. The equilibrium parameters for ethidium bromide complex formation with DNA are calculated: the
coupling constant for the dye with the biopolymer, K
1 = (232 ± 16)⋅103 M−1, and the number of base pairs of the biopolymer participating in bonding with the ligand, n
1 = 3.6 ± 0.2, are calculated. Given these values, it is suggested that under these experimental conditions there are two types
of bonding between ethidium bromide and the nucleic acid — intercalation and “external” bonds. A McGhee–von Hippel model for
a three component system and the numerical values of the parameters for molecular complex formation in two component systems
are used to calculate the bonding constant for caffeine with DNA, K
2 = 127 ± 30 M−1, and the number of base pairs of DNA which bond with caffeine, n
2 = 1.7 ± 0.2. The concentrations of ethidium bromide and caffeine in the composition of two and three component complexes
are calculated as functions of the nucleic acid content in the solution. An analysis of the concentration dependences shows
that heteroassociation of ligands has a significant effect on the reduction in the concentration of ethidium bromide–DNA complexes
in a three component system for low DNA concentrations, while at high DNA concentrations the bonding of caffeine with the
biopolymer has this effect.
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 143–151, January–February 2009. 相似文献
3.
S. F. Baranovskii P. A. Bolotin M. P. Evstigneev D. N. Chernyshev 《Journal of Applied Spectroscopy》2008,75(2):251-260
We have used spectrophotometry to study self-association and complexation with DNA by organic heterocyclic compounds in the
acridine and phenothiazine series: proflavin, thionine, and methylene blue. Based on the experimental concentration dependences
of the molar absorption coefficient of the molecules in an aqueous buffer solution (0.01 M NaCl, 0.01 M Na2EDTA, 0.01 M Tris, pH 7.4, T = 298 K), we have determined the equilibrium dimerization constants for the dyes and the DNA
complexation parameters using the Scatchard and McGhee-von Hippel models. The observed increase in the cooperativity parameters
as the dimerization constants of the ligands increase allowed us to hypothesize that the same interactions occur between dye
molecules adsorbed on DNA as in their self-association. The equilibrium DNA-binding constants for the ligands, obtained using
the McGhee-von Hippel cooperative model, are (20.9 ± 2.7)·103 M−1 for proflavin and (33.8 ± 4.1)·103 M−1 for thionine. Using the Scatchard model, taking into account intercalation and “external” binding of ligands with DNA, we
determined the DNA complexation constants for methylene blue: (26.4 ± 4.6)·103 and (96 ± 17)·103 M−1 respectively. Based on analysis of the data obtained, we hypothesized that the predominant type of binding with DNA is intercalation
binding in the case of proflavin and thionine, and “external” binding with the DNA surface in the case of methylene blue.
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 242–249, March–April, 2008. 相似文献
4.
The third-order elastic constants of single crystal GaSb are determined using ultrasonic pulse interferometer at 10 MHz. The
constants at 300°K, in units of 1011 N.m.−2, are Cl11 = ™ 4 ·75 ± 0·06 C144 = + 0·50 ± 0·25 C113 = ™ 3 ·08 ± 0·02 C166 = ™ 2·16 ± 0·13 C123 = ™ 0 ·44 ± 0·29 C456 = ™ 0·25 ± 0·15 These constants are used to evaluate the three anharmonic first and second neighbour force constants based
on modified Keating’s model. The constants are (in units of 1011 N.m−2)γ=− 2·406;δ=0·407;ε=−0·222. 相似文献
5.
M. V. Zagidullin N. A. Khvatov M. S. Malyshev 《Russian Journal of Physical Chemistry B, Focus on Physics》2011,5(6):969-973
The results of our experimental study of the kinetics of formation of O2(1Σ) molecules in energy-exchange reactions O2(1Δ) + I(5
p,2
P
1/2) and O2(a,1Δ) + O2(a,1Δ) are presented. The ratio of rate constants was obtained for these reactions (4800 ± 300). Setting the rate constant of
the deactivation of O2(1Σ) molecules on CO2 molecules at 4.1 · 10–13 cm3/s, we evaluated the rate constants for these reactions at a temperature of approximately 330 K: (1.7 ± 0.2) · 10−13 and (3.6 ± 0.5) · 10−17 cm3/s, respectively. 相似文献
6.
A precise knowledge of the Newtonian gravitational constant G has an important role in physics and is of considerable meteorological interest. Although G was the first physical constant to be introduced and measured in the history of science, it is still the least precisely
determined of all the fundamental constants of nature. The 2002 CODATA recommended value for G, G = (6.6742 ± 0.0010) × 10−11m3 · kg−1 · s−2, has an uncertainty of 150 parts per million (ppm), much larger than that of all other fundamental constants. Reviewed here
is the status of our knowledge of the absolute value of G, methods for determining G, and recent high precision experiments for determining G. 相似文献
7.
B. Hoekstra F. van Doveren J. M. Robertson 《Applied Physics A: Materials Science & Processing》1977,12(3):261-263
The magnetostriction constants of Y2.85La0.15Fe3.75Ga1.25O12 epilayers have been measured by observing the shift of the resonance line of a thin film which is stressed by three-point
bending. The result is λ111=−(0.75±0.15) × 10−6 and λ100=−(0.4±0.1) × 10−6 which is in agreement with the measurements on bulk single crystals. This result indicates that there is no growth induced
contribution to the magnetostriction in thin films of this garnet grown by liquid phase epitaxy. 相似文献
8.
J. R. Kempton R. F. Marzke D. G. Fleming A. C. Gonzalez S. K. Leung J. J. Pan P. W. Percival M. Senba A. Tempelmann 《Hyperfine Interactions》1991,65(1-4):811-817
Results of the first μSR studies using Merck FO Optipur silica powder, which contains paramagnetic impurities at the ppb level
and has a surface area of 610±20 m2/g. are reported. Above 20 K, the transverse field muonium relaxation rate is roughly constant at 0.5 μs−1. Upon the addition of oxygen at ppm levels, the relaxation rate increases linearly with O2 concentration in the temperature range from 40–100 K yielding two-dimensional depolarization rate constants on the order
of 10−4 cm2 molecule−1 s−1. As the temperature is increased further, both oxygen and muonium desorb from the surface yielding a three-dimensional rate
constants at 300 K of 3.1(3)×10–10−10 cm3 molecule−1 s−1, in agreement with the gas phase value. Longitudinal field measurements suggest that MuO2 is formed and is able to spin exchange with other oxygen molecules. 相似文献
9.
The interaction of three common herbicides, paraquat, acifluorfen and alachlor, with spinach chloroplast photosystem II (PS II) was investigated by measuring1H nuclear magnetic resonance spin-lattice relaxation rates, transient nuclear Overhauser effect (NOE) and NOE spectroscopy (NOESY) spectra. Binding to PS II was detected by (i) the enhancement of single-selective relaxation rates and (ii) the decrease in the optimal mixing time providing maximal cross-peak intensity in NOESY spectra. Titration of relaxation enhancements was used to calculate the dissociation constants (K d) from the bound state for paraquat (K d = 292 ± 71 μM−1) and acifluorfen (K d = 311 ± 58 μM−1). A similarK d was apparent for alachlor. Double-selective relaxation rates allowed the isolation of dipolar relaxation terms between selected proton pairs wherefrom dynamic features of the bound state were evaluated. In all cases the motional correlation time of bound herbicide (τc = 0.1−0.4 ns at 300 K) was found two orders of magnitude slower than in the free-solution state. In the case of alachlor the E and Z isomers were observed to bind differently to PS II and a change in conformation could be hypothesized. 相似文献
10.
I. N. Nichiporovich S. M. Bachilo A. P. Losev G. D. Egorova 《Journal of Applied Spectroscopy》1999,66(6):917-922
It was established that in aqueous solutions of anionic porphyrins the processes of triplet-triplet (T-T) annihilation are
absent (K2<2.5·105 M−1 sec−1), while a delayed annihilation fluorescence can be detected for these porphyrins in methanol (K2≊3.5·107 M−1 sec−1) and for their lipophilic analogs in organic solutions (K
2≊2.5·109 M−1 sec−1), and the kinetics of absorption of the latter porphyrins in triplet states is dependent on the intensity of the exciting
radiation. The extremely small constant of T-T annihilation of anionic porphyrins can be due to the formation of a relatively
dense solvate shell consisting of water molecules around the charged groups of the porphyrin molecules, which increases steric
barriers and thus prevents an exchange-resonance transfer of energy between triplet excited molecules in aqueous solutions.
It is also shown that porphyrin molecules can electrostatically repel one another when in their structure there are charged
groups.
To whom correspondence should be addressed.
Deceased.
Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70 F. Skorina Ave., Minsk, 220072, Belarus;
e-mail: llum@imaph.bas-net.by. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 791–795, November–December,
1999. 相似文献
11.
Experimental data on the spin-exchange rate constants for the He(23
S
1)-Na(32
S
1/2) system are reported for the first time. Measurements show that the spin-exchange rate constant is C
se
= (23 ± 11) × 10−10 cm3 s−1 and the chemical ionization rate constant is C
si
= (29 ± 14) × 10−10 cm3 s−1 at a temperature of 420 K. The results are compared with the data calculated from the rate constants. 相似文献
12.
Jean Y. C. Ganti R. L. Cheng K. L. Venkateswaran K. Walker D. C. 《Hyperfine Interactions》1986,32(1-4):813-817
The bimolecular rate constants for muonium addition to ethene (CH2=CH2) in hydrocarbon liquids were found to be ∼2×1010 M−1s−1. These rate constants change with temperature in accordance with the Arrhenius equation; but the energy barrier to reaction
(Ea) in 2-methylbutane is much less than that for viscous flow. This suggests either non-classical interaction rates stemming
from the quantum character for muonium, or non-Stokes-Einstein behavior. 相似文献
13.
The kinetics of the optical orientation of atoms in a helium-cesium gas-discharge plasma are considered, and kinetic equations
describing the optical orientation of atoms in the case of two simultaneously occurring processes, viz., an elastic process
(spin exchange) and an inelastic process (chemi-ionization), are derived. The rate constants of these processes are determined
experimentally: C
se=(2.8±0.8)×10−9 cm3s−1, C
ci=(1.0±0.3)×10−9 cm3s−1.
Zh. Tekh. Fiz. 69, 36–40 (September 1999) 相似文献
14.
Alonso A Almendral MJ Curto Y Criado JJ Rodríguez E Manzano JL 《Journal of fluorescence》2007,17(4):390-400
The flow injection technique is applied to study the binding to DNA of new platinum complexes—E1: ethylenediaminechlorocholylglycinateplatinum(II): [PtCl(CG)(en)], C54H92O12Pt and E2: ethylenediaminebischolylglycinateplatinum(II): [Pt(CG)2(en)], C28H50ClN3O6Pt—derived from cisplatin in which the exchangeable ligands were replaced by bile acids, such that these anticancer drugs
have less toxicity and less resistance is developed towards them. Both compounds are fluorescent and their fluorescence is
enhanced when they form adducts with DNA, a property that is extremely useful for monitoring the cytotoxic activity and their
mechanisms of action. The binding parameters to DNA of E1 [apparent intrinsic binding constant KE1: (11.2 ± 0.4) × 103 M−1 and maximum number of binding sites per nucleotide, n
E1: 0.121 ± 2 × 10−3) and E2 (KE2: 9.2 ± 0.7) × 103 M−1 and n
E2 0.098 ± 2 × 10−3] were determined following the Scatchard method and the type of binding was studied experimentally through the modifications
introduced by each of the compounds into the ethidium bromide–DNA bond. 相似文献
15.
The spin exchange of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and the radical anion of tetracyanoethene (TCNE), with iron
acetylacetonate, Fe(acac)3, was investigated as a function of solvent viscosity and temperature by X-band EPR spectroscopy. Acetone, methanol, ethanol,
1-propanol, 1-pentanol, 1-hexanol, 1-octanol, and chloroform were used as solvents because they provide a wide range of viscosity.
The spin exchange rate constants measured in the different solvents ranged from 3 × 108 to 8 × 109 M−1 s−1, and from 7 × 108 to 1 × 1010 M−1 s−1 for the TEMPO/Fe(acac)3 and the TCNE/Fe(acac)3 systems, respectively. The spin exchange rate constants, k
e, are compared with the corresponding diffusion rate constants. It was found that the k
e values correlate well with those of diffusion and hence the intermolecular spin exchange is strongly diffusion-controlled.
The activation energies and pre-exponential factors are calculated from the Arrhenius plots. 相似文献
16.
The luminescence kinetics of the Cd II ion at a wavelength of 441.6 nm has been studied experi-mentally in a high-pressure
He-Cd mixture in the presence of Ar, Ne, Xe, and CCl4 impurities. Cadmium ions were excited through the bombardment of a cadmium foil heated up to 240°C by a pulsed electron beam
with an electron energy of 150 keV, a pulse duration of 3 ns, and a current of 500 A. The constants of collisional quenching
of the Cd II 5s
2
2
D
5/2 level by Ar, Ne, and Xe atoms and CCl4 molecules and the integral luminescence quenching constants of this level in the helium medium by these impurity gases have
been determined. The constants of collisional quenching appeared to be 8.1 × 10−12 (Ar), 1.2 × 10−12 (Xe), 1.5 × 10−13 (Ne), and 1.8 × 10−10 cm3/s (CCl4, for λ = 325 nm), while the integral constants were found to be, respectively, 4.1 × 10−11, 3.4 × 10−11, 9.5 × 10−12, 1.4 × 10−9 cm3/s for Ar, Ne, Xe, and CCl4 at a buffer gas pressure of 1 atm.
Original Russian Text ? A.I. Miskevich, Liu Tao, 2009, published in Optika i Spektroskopiya, 2009, Vol. 107, No. 1, pp. 45–49. 相似文献
17.
Yu. A. Troyan S. G. Arakelyan A. V. Belyaev A. P. Ierusalimov E. B. Plekhanov A. Yu. Troyan 《Physics of Particles and Nuclei Letters》2012,9(1):47-53
We present the results of a search for and study of the resonance effects in the system of π+π− from the reaction np → npπ+π− at the momentum of quasi-monochromatic neutrons P
n
= (5.20 ± 0.12) GeV/c from the data obtained in an exposure of the 1-m hydrogen bubble chamber of Veksler and Baldin Laboratory of High Energies,
Joint Institute for Nuclear Research (VBLHE JINR). After the supplementary selection of the events where a secondary proton
was emitted in the forward hemisphere in the general c.m.s. of the reaction (cosθ*
p
> 0) in the effective mass spectrum of π+π− combinations, we found nine peculiarities at the masses (350 ± 3), (408 ± 3), (489 ± 3), (579 ± 5), (676 ± 7), (762 ± 11),
(878 ± 7), (1036 ±13), and (1170 ± 11) MeV/c
2 with experimental widths of no more than several tens of MeV/c
2. We carried out a direct measurement of the spins of resonances and also obtained other quantum numbers. All of these peculiarities
have a similar set of quantum numbers I
G
(J
PC
) = 0+ (0++). We investigated a sequence of scalar-isoscalar resonances f
0(σ0) with masses in the range M ≤ 1200 MeV/c
2. We found a phenomenological dependence of the resonance mass on its number. This dependence covered not only the resonances
shown in this paper, but also those present in PDG tables with quantum numbers of f
0(σ0) mesons. 相似文献
18.
Electroconductivity of BaCe0.9Nd0.1O3−α was studied as a function of the composition of the H2+H2O+Ar mixture and temperature in the interval from 873 to 1173 K. It was shown that the electroconductivity was independent
of PH2 (0.97 to 0.10 atm) and PO2 (10−21 to 10−26 atm), but depended on PH2O (0.08 to 0.005 atm). A mathematical processing of the PH2O dependencies of the electroconductivity, which was performed in terms of a classical model of defect formation in high-temperature
proton-conducting solid electrolytes, yielded equilibrium constants of the reaction of water dissolution in BaCe0.9Nd0.1O3−α and mobilities of protons and oxygen ions. The temperature dependencies of these quantities were used to determine the mobility
activation energies of protons (Ea=34±7 kJ/mole) and oxygen ions (Ea=72±8 kJ/mole), and also the enthalpy (ΔH=−150±25 kJ/mole) and the entropy (ΔS=153±26 kJ/mole·K) of the reaction of water
dissolution in BaCe0.9Nd0.1O3−α. 相似文献
19.
Masayoshi Senba Alicia C. Gonzalez James R. Kempton Donald J. Arseneau James J. Pan Alexandra Tempelmann Donald G. Fleming 《Hyperfine Interactions》1991,65(1-4):979-986
The addition reaction Mu+NO+M→MuNO+M and the spin exchange reaction Mu(↑) +MO(↓)→Mu(↓)+NO(↑) have been measured by longitudinal
field μSR at room temperature in the presence of up to 58 atm of N2 as inert collider. The pressure dependence of the longitudinal relaxation rate due to the addition reaction (λc) demostrates that the system is still in the low pressure regime in this pressure range. The corresponding termolecular rate
constant has been determined ask
0,Mu
=(1.10±0.25)×10−32 cm6 molecules−2 s−1, almost 4 times smaller than the corresponding H atom reactionk
0,H=3.90×10−32 cm6 molecules−2 s−1 [I.M. Campbell et al., J. Chem. Soc. Faraday Trans. 1.71 (1975) 2097]. The average value of the spin exchange rate constants
in the 2.5–58 atm pressure range,k
SE=(3.16±0.06)×10−10 cm3 molecule−1 s−1, is in good agreement with previous values obtained by transverse field μSR [D.G. Fleming et al., J. Chem. Phys. 73 (1980)
2751]. 相似文献
20.
We used the spin-Hamiltonian method for the analysis of the electron paramagnetic resonance (EPR) spectrum of Fe3+ as a probe ion in (NH4)2AlF5·H2O single crystalline basic material. The theoretical expressions for the magnetic field (at which the fine structure transition lines appear) versus the angle between the magnetic field and the axis of symmetry of the magnetic complex are also given. These values were calculated by applying the perturbation theory to the second-order terms. From the experimental results (at 300 K and 9.21 GHz), the spin-Hamiltonian parameters were deduced:D=(668±10)·10−4 T,E=(−56±10)·10−4 T,a=(−54±10)·10−4 T,F=(30±10)·10−4 T. An isotropic superhyperfine structure was evidenced for the five fluorine ions. The obtained EPR data were used to determine the local symmetry of the Al3+ ion. A good agreement with X-ray diffraction measurements was found. 相似文献