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1.
Abstract

The interaction of calf-thymus DNA with trivalent Al and Ga cations, in aqueous solution at pH =6–7 with cation/DNA(P) (P=phosphate) molar ratios (r) 1/80, 1/40, 1/20, 1/10, 1/4 and 1/2 was characterized by Fourier Transform infrared (FTIR) difference spectroscopy.

Spectroscopic results show the formation of several types of cation-DNA complexes. At low metal ion concentration (r=l/80, 1/40), both cations bind mainly to the backbone PO2 group and the guanine N-7 site of the G-C base pairs (chelation). Evidence for cation chelate formation comes from major shifting and intensity increase of the phosphate antisymmetric stretch at 1222 cm-1 and the mainly guanine band at 1717 cm1. The perturbations of A-T base pairs occur at high cation concentration with major helix destabilization. Evidence for cation binding to A-T bases comes from major spectral changes of the bands at 1663 and 1609 cm-1 related mainly to the thymine and adenine in-plane vibrations. A major reduction of the B-DNA structure occurs in favor of A-DNA upon trivalent cation coordination.  相似文献   

2.
Abstract

We report the interaction of calf-thymus DNA with D-glucose, D-fructose, D-galactose and sucrose in aqueous solution at physiological pH with sugar/DNA(P)(P=phosphate) molar ratios (r) of 1/10,1/5,1,5 and 10. FTIR difference spectroscopy was used to characterize the nature of sugar-DNA interaction and correlations between spectral changes and structural variations for both sugar and DNA complexes have been established.

FTIR difference spectroscopic results showed major sugar interaction (H-bonding) with the P02 groups of the backbone at low sugar concentrations (r= 1/10 and 1/5). Such interaction was characterized by the shift and the intensity variations of the backbone P02 antisymmetric stretch at 1222 cm?1, which resulted in a major helical stability of DNA duplex. As sugar concentration increased, carbohydrate binding to DNA bases occurred. Evidence for this comes from major shiftings of the sugar O-H stretching vibrations at 3500–3200 cm?1, and sugar C-O stretches and OH bending modes at 1450–1000 cm”. Similarly, shifting and intensity variations of several DNA in-plane vibrations at 1717 (G,T), 1663 (T,G,A,C) and 1492 cm?1 (C,G) were observed, that are characterized by the presence of sugar-base interaction (via H20). The shiftings and the intensity changes of the sugar OH stretching modes at 35003200 cm?1 are also indicative of the rearrangements of the sugar intermolecular H-bonding network, on DNA complex formation. A partial B to A conformational transition was observed for DNA molecule on sugar complexation, whereas carbohydrate binding occurred via both a- and β-anomeric structures.  相似文献   

3.
The interaction of calf thymus DNA with Cu2+and Pb2+ was studied in aqueous solution at pH 6.5 with metal/DNA (P) (P = phosphate) molar ratios (r) 1/80, 1/40, 1/20, 1/10, 1/4, 1/2, and 1, using Fourier Transform ir (FTIR) spectroscopy. Correlations between the ir spectral changes, metal ion binding mode, DNA condensation, and denaturation, as well as conformational features, were established. Spectroscopic evidence has shown that at low metal/DNA (P) molar rations 1/80 and 1/40, copper and lead ions bind mainly to the PO of the backbone, resulting in increased base-stacking interaction and duplex stability. The major copper ion base binding via G-C base pairs begins at r > 1/40, while the lead ion base binding occurs at r > 1/20 with the A-T base pairs. The denaturation of DNA begins at r = 1/10 and continues up to r = 1/2 in the presence of copper ions, whereas a partial destabilization of the helical structure was observed for the lead ion at high metal ion concentration (r = 1/2). Metal-DNA binding also results in DNA condensation. No major departure from the B-family structure was observed, upon DNA interaction with these metal ions. © 1993 John Wiley & Sons, Inc.  相似文献   

4.
Abstract

Ascorbic acid and divalent iron salts have been widely used to investigate the effects of reactive oxygen species in different biological targets such as nucleic acids, proteins and lipids. This study was designed to examine the interaction of yeast RNA with vitamin C in aqueous solution at physiological pH with drug/RNA(P)(P=phosphate) molar ratios of r= 1/80, 1/40, 1/20, 1/10, 1/4 and 1/2. Absorption spectra and Fourier transform infrared (FTIR) difference spectroscopy were used to determine the ascorbate binding mode, binding constant, sequence selectivity and RNA secondary structure in aqueous solution.

Spectroscopic evidence showed that at low drug concentration (r=1/80 and 1/40), no major ascorbate-RNA interaction occurs, while at higher drug concentrations (r>1/40), a major drug-RNA complexation was observed through both G-C and A-U base pairs and the backbone phosphate groups with k=31.80 M?1. Evidence for this comes from large perturbations of the G-C vibrations at 1698 and 1488 cm?1 and the A-U bands at 1654 and 1608 cm?1 as well as the phosphate antisymmetric stretch at 1244 cm?1. At r>1/10, minor structural changes occur for the ribose-phosphate backbone geometry with RNA remaining in the A- family structure. The drug distributions around double helix were about 55% with G-C, 33% A-U and 12% with PO2 groups. A comparison between ascorbate-RNA and ascorbate-DNA complexes showed minor differences. The ascorbate binding (H-bonding) is via anion CO and OH groups.  相似文献   

5.
The search for earth‐abundant and high‐performance electrode materials for sodium‐ion batteries represents an important challenge to current battery research. 2D transition metal dichalcogenides, particularly MoS2, have attracted increasing attention recently, but few of them so far have been able to meet expectations. In this study, it is demonstrated that another phase of molybdenum sulfide—amorphous chain‐like MoS3—can be a better choice as the anode material of sodium‐ion batteries. Highly compact MoS3 particles infiltrated with carbon nanotubes are prepared via the facile acid precipitation method in ethylene glycol. Compared to crystalline MoS2, the resultant amorphous MoS3 not only exhibits impressive gravimetric performance—featuring excellent specific capacity (≈615 mA h g?1), rate capability (235 mA h g?1 at 20 A g?1), and cycling stability but also shows exceptional volumetric capacity of ≈1000 mA h cm?3 and an areal capacity of >6.0 mA h cm?2 at very high areal loadings of active materials (up to 12 mg cm?2). The experimental results are supported by density functional theory simulations showing that the 1D chains of MoS3 can facilitate the adsorption and diffusion of Na+ ions. At last, it is demonstrated that the MoS3 anode can be paired with an Na3V2(PO4)3 cathode to afford full cells with great capacity and cycling performance.  相似文献   

6.
The interaction of HCl with calf thymus DNA was investigated in aqueous solution at pH 7-2 with H+/DNA(P)(P:phosphate) molar ratios (r) of 1/80, 1/40, 1/20, 1/10, 1/4, 1/2, and 1, using Fourier Transform (FTIR) difference spectroscopy. Correlations between spectral changes, proton binding mode, DNA denaturation, and conformational variations are established. A comparison was also made between their spectra of denaturated DNA, in the presence of proton and Cu ions with similar cation concentrations. The FTIR difference spectroscopic results have shown that at low proton concentrations of r = 1/80 and 1/40 (pH 7–5), no major spectral changes occur for DNA, and the presence of H+ results in an increased base-stacking interaction and helical stability. At higher proton concentrations of r > 1/40, the proton binding to the cytosine and adenine bases begins with major destabilization of the helical duplex. As base protonation progresses, a B to C conformational conversion occurs with major DNA spectral changes. Protonation of guanine bases occurs at a high cation concentration r > 1/2 (pH < 3) with a major increase in the intensity of several DNA in-plane vibrations. Copper ion complexation with DNA exhibits marked similarities with proton at high cation concentrations (r > 1/10), whereas at low metal ion concentrations, copper–PO2 and copper–guanine N-7 bindings are predominant. No major DNA conformational transition was observed on copper ion complexation. © 1995 John Wiley & Sons, Inc.  相似文献   

7.
Infrared spectrum of a DNA-RNA hybrid   总被引:2,自引:0,他引:2  
S Higuchi  M Tsuboi  Y Iitaka 《Biopolymers》1969,7(6):909-916
The infrared absorption spectrum in the 4000–400 cm? region of an oriented film of a DNA–RNA hybrid in its undeuterated and deuterated states was observed with the polarized radiation. Most of the stronger bands found in the double-helical DNA's and double-helical RNA's are identified in the spectrum of the hybrid. The absorption band at 1225 cm?1 shows a perpendicular dichroism and that at 1085 cm?1 shows almost no dichroism. These facts indicate that the orientation of the group with respect to the helix axis in the hybrid structure is not entirely the same as that in the double-helical Na DNA at, 75% RH., although the x-ray diffraction pattern of the hybrid is quite similar to that of the DNA A form. The PO2? orientation is not the same as that in the double-helical RNA either. The observed dichroism is explained, however, by considering that the PO2? group in the RNA moiety takes nearly the same orientation as that in the double-helical RNA, and the PO2? group in the DNA moiety takes nearly the same as that in the double-helical DNA.  相似文献   

8.
C Zimmer  G Luck  H Triebel 《Biopolymers》1974,13(3):425-453
The effects of metal ions of the first-row transition and of alkaline earth metals on the DNA helix conformation have been studied by uv difference spectra, circular dichroism, and sedimentation measurements. At low ionic strength (10?3 M NaClO4) DNA shows a maximum in the difference absorption spectra in the presence of Zn2+, Mn2+, Co2+, Cd2+, and Ni2+ but not with Mg2+ or Ca2+. The amplitude of this maximum is dependent on GC content as revealed by detailed studies of the DNA-Zn2+ complex of eight different DNA's. Pronounced changes also occur in the CD spectra of DNA transition metal complexes. A transition appears up to a total ratio of approximately 1 Zn2+ per DNA phosphate at 10?3 M NaClO4; then no further change was observed up to high concentrations. The characteristic CD changes are strongly dependent on the double-helical structure of DNA and on the GC content of DNA. Differences were also observed in hydrodynamic properties of DNA metal complexes as revealed by the greater increase of the sedimentation coefficient of native DNA in the presence of transition metal ions. Spectrophotometric acid titration experiments and CD measurements at acidic pH clearly indicate the suppression of protonation of GC base-pair regions on the addition of transition metal ions to DNA. Similar effects were not observed with DNA complexes with alkaline earth metal ions such as Mg2+ or Ca2+. The data are interpreted in terms of a preferential interaction of Zn2+ and of other transition metal ions with GC sites by chelation to the N-7 of guanine and to the phosphate residue. The binding of Zn2+ to DNA disappears between 0.5 M and 1 M NaClO4, but complex formation with DNA is observable again in the presence of highly concentrated solutions of NaClO4 (3?7.2 M NaClO4) or at 0.5 to 2 M Mn2+. At relatively high cation concentration Mg2+ is also effective in changing the DNA comformation. These structural alterations probably result from both the shielding of negatively charged phosphate groups and the breakdown of the water structure along the DNA helix. Differential effects in CD are also observed between Mn2+, Zn2+ on one hand and Mg2+ on the other hand under these conditions. The greater sensitivity of the double-helical conformation of DNA to the action of transition metal ions is due to the affinity of the latter to electron donating sites of the bases resulting from the d electronic configuration of the metal ions. An order of the relative phosphate binding ability to base-site binding ability in native DNA is obtained as follows: Mg2+, Ba2+, < Ca2+ < Fe2+, Ni2+, Co2+ < Mn2+, Zn2+ < Cd2+ < Cu2+. The metal-ion induced conformational changes of the DNA are explained by alternation of the winding angle between base pairs as occurs in the transition from B to C conformation. These findings are used for a tentative molecular interpretation of some effects of Zn2+ and Mn2+ in DNA synthesis reported in the literature.  相似文献   

9.
Abstract

The interaction of DNA and RNA with Cu(II), Mg(II), [Co(NH3)6]3+ [Co(NH3)5Cl]2+ chlorides and, cis- and trans-Pt(NH3)2Cl2 (CIS-DDP, trans-DDP) has been studied by Fourier Transform Infrared (FT-IR) spectroscopy and a correlation between metal-base binding and conformational transitions in the sugar pucker has been established. It has been found that RNA did not change from A-form on complexation with metals, whereas DNA exhibited a B to Z transition. The marker bands for the A-form (C′3-endo-anti conformation) were found to be near 810–816 cm?1, while the bands at 825 and 690 cm?1 are marker bands for the B- conformation (C′2-endo, anti), The B to Z (C3-endo, syn conformation) transition is characterized by the shift of the band at 825 cm?1 to 810–816 cm?1 and the shift of the guanine band at 690 cm?1 to about 600–624 cm?1.  相似文献   

10.
Solid‐state sodium batteries (SSSBs) are promising electrochemical energy storage devices due to their high energy density, high safety, and abundant resource of sodium. However, low conductivity of solid electrolyte as well as high interfacial resistance between electrolyte and electrodes are two main challenges for practical application. To address these issues, pure phase Na3Zr2Si2PO12 (NZSP) materials with Ca2+ substitution for Zr4+ are synthesized by a sol‐gel method. It shows a high ionic conductivity of more than 10?3 S cm?1 at 25 °C. Moreover, a robust SSSB is developed by integrating sodium metal anodes into NZSP‐type monolithic architecture, forming a 3D electronic and ionic conducting network. The interfacial resistance is remarkably reduced and the monolithic symmetric cell displays stable sodium platting/striping cycles with low polarization for over 600 h. Furthermore, by combining sodium metal anode with Na3V2(PO4)3 cathode, an SSSB is demonstrated with high rate capability and excellent cyclability. After 450 cycles, the capacity of the cell is still kept at 94.9 mAh g?1 at 1 C. This unique design of monolithic electrolyte architecture provides a promising strategy toward realizing high‐performance SSSBs.  相似文献   

11.
Optimum conditions have been established for isolation of ‘cryptic’ satellite DNA from the genome of pea (Pisum sativum), using gradients of CS2SO4 containing silver ions. At an Ag+ :DNA-P ratio (R) of 0.1, and at alkaline pH, four fractions are obtained: mainband (buoyant density 1.437 g cm3; 67% of total DNA), satellite I (buoyant density 1.582 g/cm3; 7% of total DNA), satellite II (buoyant density 1.520 g/cm3, 11% of total) and satellite III (buoyant density variable between 1.45 and 1.51 g/cm3; 15% of total). The reiterated DNA content of these four fractions has been investigated by reassociation experiments conducted over a Cot range of 1 × 10?5 to 2.0. All four fractions contain at least two kinetic components; each fraction, including the mainband, consists at least partly of highly reiterated DNA. Ribosomal RNA hybridizes only to the mainband.  相似文献   

12.
J. Pilet  J. Brahms 《Biopolymers》1973,12(2):387-403
DNA-oriented samples of various origins were studied under different conditions of humidiity and sodium chloride content by means of infrared spectroscopy. (1) Oriented DNA (M. Lysodeikticus, E. coli, calf thymus and salmon sperm) films at 3–4% sodium chloride yield polarized spectra which show drastic changes at relative humidities (r.h.) between 94% and 0% indicative of conformational changes: B form → a form → disordered form The measurements of the infrared dichroism at frequencies of about 1230 cm?1 and at about 1090 cm?1 allow one to determine the orientation of the phosphate group, whereas the measurements at 1710 cm?1 characterize the base orientation. At humidities higher than 90% r.h. (B form) the bisector of OPO forms an angle of 70° relative to the helix axis, whereas at lower humidities, between 75% and 50% r.h. (A form) a rotation to about 45° is observed. Simultaneously, the 0—0 line of phosphate group changes its orientation from 55° to 65° to the helix when B → A transition takes place. The results are in general agreement with that of X-ray diffraction and allow one to determine the orientation of the phosphate group with greater precision. (2) The B–A conformational change is not observed for satellite DNA, isolated from Cancer pagurus, of which the guanine + cytosine content is below 5%. As a function of decreasing humidities, one observes the transition: B form → disordered form A diagram of conformational changes of DNA's as a function of base composition and of r.h., suggests that B–A transition will occur for DNA of relatively higher G + C content, whereas for high (A + T) content, base sequence may be of importance. The B–A transition is prevented in DNA at a relatively high or very low sodium chloride content.  相似文献   

13.
An investigation was untertaken to evaluate the nutrient status of the River Rhine (two stations) and eight of its tributaries (total of ten samplings). Determinations of the following inorganic substances were made: PO4 ?3-P; NO3 ?-N; NO2 ?-N; NH4 + -N and Cl?. In addition, pH and carbonate alkalinity were measured. Bioassays to obtain the algal growth potential (AGP) were carried out using periphyton from the River Rhine. A linear relationship could be established between NO3 ?-N and the AGP, while the AGP showed a non-linear dependence on the PO4 3?-P concentration. The critical N/P ratio for N or P limitation of the algal growth in bioassays was evaluated graphically and by calculation. The results of the two methods are in good agreement: N is the limiting factor at NO3 ?N/PO4 3?-P ratios less than 10, while P is limiting at ratios greater than 20. At values between 10 and 20 neither N nor P can be supposed with certainty to be limiting.  相似文献   

14.
Sulforaphane (SFN) is an isothiocyanate found in cruciferous vegetables with anti-inflammatory, anti-oxidant and anti-cancer activities. However, the antioxidant and anticancer mechanism of sulforaphane is not well understood. In the present research, we reported binding modes, binding constants and stability of SFN–DNA and -RNA complexes by Fourier transform infrared (FTIR) and UV–Visible spectroscopic methods. Spectroscopic evidence showed DNA intercalation with some degree of groove binding. SFN binds minor and major grooves of DNA and backbone phosphate (PO2), while RNA binding is through G, U, A bases with some degree of SFN–phosphate (PO2) interaction. Overall binding constants were estimated to be K(SFN–DNA)=3.01 (± 0.035)×104 M-1 and K(SFN–RNA)= 6.63 (±0.042)×103 M-1. At high SFN concentration (SFN/RNA = 1/1), DNA conformation changed from B to A occurred, while RNA remained in A-family structure.  相似文献   

15.
Over the last decade, Na‐ion batteries have been extensively studied as low‐cost alternatives to Li‐ion batteries for large‐scale grid storage applications; however, the development of high‐energy positive electrodes remains a major challenge. Materials with a polyanionic framework, such as Na superionic conductor (NASICON)‐structured cathodes with formula NaxM2(PO4)3, have attracted considerable attention because of their stable 3D crystal structure and high operating potential. Herein, a novel NASICON‐type compound, Na4MnCr(PO4)3, is reported as a promising cathode material for Na‐ion batteries that deliver a high specific capacity of 130 mAh g?1 during discharge utilizing high‐voltage Mn2+/3+ (3.5 V), Mn3+/4+ (4.0 V), and Cr3+/4+ (4.35 V) transition metal redox. In addition, Na4MnCr(PO4)3 exhibits a high rate capability (97 mAh g?1 at 5 C) and excellent all‐temperature performance. In situ X‐ray diffraction and synchrotron X‐ray diffraction analyses reveal reversible structural evolution for both charge and discharge.  相似文献   

16.
31P-nmr has been used to investigate the specific interaction of three divalent metal ions, Mg2+, Mn2+, and Co+2, with the phosphate groups of DNA. Mg2+ is found to have no significant effect on any of the 31P-nmr parameters (chemical shift, line-width, T1, T2, and NOE) over a concentration range extending from 20 to 160 mM. The two paramagnetic ions, Mn2+ and Co2+, on the other hand, significantly change the 31P relaxation rates even at very low levels. From an analysis of the paramagnetic contributions to the spin–lattice and spin–spin relaxation rates, the effective internuclear metal–phosphorus distances are found to be 4.5 ± 0.5 and 4.1 ± 0.5 Å for Mn2+ and Co2+, respectively, corresponding to only 15 ± 5% of the total bound Mn2+ and Co2+ being directly coordinated to the phosphate groups (inner-sphere complexes). This result is independent of any assumptions regarding the location of the remaining metal ions which may be bound either as outer-sphere complexes relative to the phosphate groups or elsewhere on the DNA, possibly to the bases. Studies of the temperature effects on the 31P relaxation rates of DNA in the absence and presence of Mn2+ and Co2+ yielded kinetic and thermodynamic parameters which characterize the association and dissociation of the metal ions from the phosphate groups. A two-step model was used in the analysis of the kinetic data. The lifetimes of the inner-sphere complexes are 3 × 10?7 and 1.4 × 10?5 s for Mn2+ and Co2+, respectively. The rates of formation of the inner-sphere complexes with the phosphate are found to be about two orders of magnitude slower than the rate of the exchange of the water of hydration of the metal ions, suggesting that expulsion of water is not the rate-determining step in the formation of the inner-sphere complexes. Competition experiments demonstrate that the binding of Mg2+ ions is 3–4 times weaker than the binding of either Mn2+ or Co2+. Since the contribution from direct phosphate coordination to the total binding strength of these metal ion complexes is small (~15%), the higher binding strength of Mn2+ and Co2+ may be attributed either to base binding or to formation of stronger outer-sphere metal–phosphate complexes. At high levels of divalent metal ions, and when the metal ion concentration exceeds the DNA–phosphate concentration, the fraction of inner-sphere phosphate binding increases. In the presence of very high levels of Mg2+ (e.g., 3.1M), the inner-sphere ? outer-sphere equilibrium is shifted toward ~100% inner-sphere binding. A comparison of our DNA results and previous results obtained with tRNA indicates that tRNA and DNA have very similar divalent metal ion binding properties. A comparison of the present results with the predictions of polyelectrolyte theories is presented.  相似文献   

17.
Radioisotopes that emit electrons (beta particles), such as radioiodine, can effectively kill target cells, including cancer cells. Aqueous 32P[PO4] is a pure beta-emitter that has been used for several decades to treat non-malignant human myeloproliferative diseases. 32P[PO4] was directly compared to a more powerful pure beta-emitter, the clinically important 90Y isotope. In vitro, 32P[PO4] was more effective at killing cells than was the more powerful isotope 90Y (P ≤ 0.001) and also caused substantially more double-stranded DNA breaks than did 90Y. In vivo, a single low-dose intravenous dose of aqueous elemental 32P significantly inhibited tumor growth in the syngeneic murine cancer model (P ≤ 0.001). This effect is exerted by direct incorporation into nascent DNA chains, resulting in double-stranded breakage, a unique mechanism not duplicatable by other, more powerful electron-emitting radioisotopes. 32P[PO4] should be considered for human clinical trials as a potential novel anti-cancer drug.  相似文献   

18.
When 1, 10-phenanthroline at 10?4 mole/kg was administered intraperitoneally to C3H mice, a significant decrease of (32P) Na2HPO4 incorporation into splenic DNA and RNA was noted within 15 min. The same dose or higher was required to significantly inhibit the incorporation of (5-3H) uridine and (methyl-3H) thymidine into splenic nucleic acid. 1, 10-phenanthroline also decrease the incorporation of the 32P into DNA and RNA in 6C3HED ascites tumor. 1, 7-phenanthroline, a non-chelating analogue at 10?4 mole/kg, less effectively altered the rate of the 32P incorporation into splenic nucleic acid within 15 min, but significantly inhibited the incorporation within 1 hr.  相似文献   

19.
20.
Abstract

Fourier Transform Infrared (FT-IR) spectra of solid samples of DNA and RNA obtained from freeze-drying at solid CO2 and liquid nitrogen temperatures, have been recorded and correlation between the conformational transitions and spectral changes is proposed. It is concluded that an equilibrium exists between A, B and Z conformations at low temperatures for the DNA molecule, which is temperature dependent, whereas the RNA molecule exhibits only the A conformation. The results have been compared with the metal-adducts of DNA and RNA, where one of the conformations is predominant.

Marker infrared bands for the B conformer have been found to be the strong band at 825 cm?1 (sugar conformer mode) and a band with medium intensity at 690 cm?1 (guanine breathing mode). The A conformation showed characteristic bands at 810 and 675 cm?1. The B to Z conformational transition was characterized by the strong absorption bands near 820-810 cm?1 and at 665-600 cm?1.  相似文献   

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