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1.
2.
The dissociation kinetics of a series of complementary and noncomplementary DNA duplexes, (TGCA)(2) (3-), (CCGG)(2) (3-), (AATTAAT)(2) (3-), (CCGGCCG)(2) (3-), A(7).T(7) (3-), A(7).A(7) (3-), T(7).T(7) (3-), and A(7).C(7) (3-) were investigated using blackbody infrared radiative dissociation in a Fourier transform mass spectrometer. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained. Activation energies range from 1.2 to 1.7 eV, and preexponential factors range from 10(13) to 10(19) s(-1). Dissociation of the duplexes results in cleavage of the noncovalent bonds and/or cleavage of covalent bonds leading to loss of a neutral nucleobase followed by backbone cleavage producing sequence-specific (a - base) and w ions. Four pieces of evidence are presented which indicate that Watson-Crick (WC) base pairing is preserved in complementary DNA duplexes in the gas phase: i. the activation energy for dissociation of the complementary dimer, A(7).T(7) (3-), to the single strands is significantly higher than that for the related noncomplementary A(7).A(7) (3-) and T(7).T(7) (3-) dimers, indicating a stronger interaction between strands with a specific base sequence, ii. extensive loss of neutral adenine occurs for A(7).A(7) (3-) and A(7).C(7) (3-) but not for A(7).T(7) (3-) consistent with this process being shut down by WC hydrogen bonding, iii. a correlation is observed between the measured activation energy for dissociation to single strands and the dimerization enthalpy (-DeltaH(d)) in solution, and iv. molecular dynamics carried out at 300 and 400 K indicate that WC base pairing is preserved for A(7).T(7) (3-) duplex, although the helical structure is essentially lost. In combination, these results provide strong evidence that WC base pairing can exist in the complete absence of solvent.  相似文献   

3.
The one-electron reduction of [Pd3(C7H7)2(CH3CN)3][BF4]2 in acetonitrile resulted in the formation of the dimer dication [Pd6(C7H7)4(CH3CN)4][BF4]2, whose structure containing a novel bitriangle hexapalladium skeleton was determined by X-ray crystallographic analysis. The dimer is stable in CD3CN at ambient temperature for several days but is highly air-sensitive. Similarly, the cycloheptatriene tripalladium complex [Pd3(C7H7R)2(CH3CN)3][BF4]2 (R = H, t-Bu) dimerized upon one-electron reduction. Both monomer and dimer of cycloheptatriene complexes were structurally determined by X-ray crystallographic analyses.  相似文献   

4.
From Iris delavayi collected in the northwestern Yunnan Province of China, eight iridal-type triterpenoids were isolated, three of which were new. Both 2(7)Z- and 2(7)E-iridals were isolated in about equal amounts from the sample collected at Laojunshan, while only 2(7)Z-iridals were isolated from samples collected in Shangrila area, indicating the presence of chemical diversity in the species.  相似文献   

5.
Ion mobility measurements have been used to examine the conformations present for unsolvated Ac-(AG)(7)A+H(+) and (AG)(7)A+H(+) peptides (Ac = acetyl, A = alanine, and G = glycine) over a broad temperature range (100-410 K). The results are compared to those recently reported for Ac-A(4)G(7)A(4)+H(+) and A(4)G(7)A(4)+H(+), which have the same compositions but different sequences. Ac-(AG)(7)A+H(+) shows less conformational diversity than Ac-A(4)G(7)A(4)+H(+); it is much less helical than Ac-A(4)G(7)A(4)+H(+) at the upper end of the temperature range studied, and at low temperatures, one of the two Ac-A(4)G(7)A(4)+H(+) features assigned to helical conformations is missing for Ac-(AG)(7)A+H(+). Molecular dynamics simulations suggest that the different conformational preferences are not due to differences in the stabilities of the helical states, but differences in the nonhelical states: it appears that Ac-(AG)(7)A+H(+) is more flexible and able to adopt lower energy globular conformations (compact random looking three-dimensional structures) than Ac-A(4)G(7)A(4)+H(+). The helix to globule transition that occurs for Ac-(AG)(7)A+H(+) at around 250-350 K is not a direct (two-state) process, but a creeping transition that takes place through at least one and probably several intermediates.  相似文献   

6.
We successfully synthesized two enantiomers of bicyclic enones, (7R,7aR)- and (7S,7aS)-9, from the hemiacetal 2a, which we first synthesized from the symmetrical diketone 1a via diastereoselective carbon-oxygen bond formation between one of the carbonyl groups and the chiral alcohol on the C2 side chain in a 2,2-disubstituted 1,3-cycloalkanedione derivative. We also report the total synthesis of natural (+)-lycopladine A [(+)-6] from (7R,7aR)-9 and the formal synthesis of unnatural (-)-lycopladine A [(-)-6] from (7S,7aS)-9.  相似文献   

7.
We have established cation/anion coupling reactions between the tropylium ligand in [M(eta7-C7H7)(CO)3]+ (M = Cr, W) and the reductively activated eta4-benzene ligand in [Mn(eta4-C6H6)(CO)3]- (3-) to form [M(CO)3(mu2-eta6:eta5-C7H7-C6H6)Mn(CO)3]; [Cr(CO)3(mu2-eta6:eta5-C7H7-C6H6)Mn(CO)3] can be further reduced to [Cr(CO)3(mu2-eta5:eta4-C7H7-C6H6)Mn(CO)3]2-, in which the tropylium and benzene ligands have undergone a [2 + 2] cross coupling reaction.  相似文献   

8.
Five bis(tert-butylnitroxide) diradicals connected by a silole (7 a-d) or a thiophene (12) ring as a coupler were studied. Compound 12 crystallizes in the orthorhombic space group Pna2(1) with a = 20.752(5), b = 5.826(5), and c = 34.309(5) A. X-ray crystal structure determination, electronic spectroscopy, variable-temperature EPR spectroscopy, SQUID measurements and DFT computations (UB3LYP/6-31+G*) were used to study the molecular conformations and electronic spin coupling in this series of molecules. Whereas compounds 7 b, 7 c, and 7 d are quite stable both in solution and in the solid state, 7 a and 12 undergo a partial electronic rearrangement to both a diamagnetic quinonoidal form and a monoradical species owing to the fact that they correspond to the open form of a pi-conjugated Kekulé structure. In the solid state, magnetic measurements indicate that the diradicals are all antiferromagnetically coupled, as expected from their topology. These interactions are best reproduced by means of a "Bleaney-Bowers" model that gives values of J = -142.0 cm(-1) for 7 a, -1.8 cm(-1) for 7 b, -1.3 cm(-1) for 7 c, -4.2 cm(-1) for 7 d, and -248.0 cm(-1) for 12. The temperature dependence of the EPR half-field transition in frozen dichloromethane solutions is consistent with singlet ground states and thermally accessible triplet states for diradicals 7 b, 7 c, and 7 d with DeltaE(T-S) values of 3.48, 2.09, and 8 cm(-1), respectively. No evidence of a populated triplet state was found for diradicals 7 a and 12. Similarities between the DeltaE(T-S) and J values (DeltaE(T-S) = -2 J) clearly show the intramolecular origin of the observed antiferromagnetic interaction. Analyses of the data with a "Karplus-Conroy"-type equation enabled us to establish that the silole ring, as a whole, allows a more efficient magnetic coupling of the two nitroxide radicals attached to its 2,5-positions than the thiophene ring. This superiority probably originates from the nonaromaticity of the silole which thus permits a better magnetic interaction through it. DFT calculations also support the experimental results, indicating that the magnetic exchange pathway preferentially involves the carbon pi system of the silole.  相似文献   

9.
X-ray structural determinations and computational studies were used to investigate halogen interactions in two halogenated oxindoles. Comparative analyses of the interaction energy and the interaction properties were carried out for Br···Br, C-H···Br, C-H···O and N-H···O interactions. Employing Møller–Plesset second-order perturbation theory (MP2) and density functional theory (DFT), the basis set superposition error (BSSE) corrected interaction energy (Eint(BSSE)) was determined using a supramolecular approach. The Eint(BSSE) results were compared with interaction energies obtained by Quantum Theory of Atoms in Molecules (QTAIM)-based methods. Reduced Density Gradient (RDG), QTAIM and Natural bond orbital (NBO) calculations provided insight into possible pathways for the intermolecular interactions examined. Comparative analysis employing the electron density at the bond critical points (BCP) and molecular electrostatic potential (MEP) showed that the interaction energies and the relative orientations of the monomers in the dimers may in part be understood in light of charge redistribution in these two compounds.  相似文献   

10.
We observed the low-frequency Raman-active intermolecular vibrational modes of 7-azaindole in CCl(4) by femtosecond Raman-induced Kerr effect spectroscopy. To understand the dynamical aspects and vibrational modes of 7-azaindole in the solution, the ultrafast dynamics of 1-benzofuran in CCl(4) was also examined as a reference and ab initio quantum chemistry calculations were performed for 7-azaindole and 1-benzofuran. The cooperative hydrogen-bonding vibrational bands of 7-azaindole dimer in CCl(4) appeared at 89 cm(-1) and 105 cm(-1) represent the overlap of stagger and wheeling modes and the intermolecular stretching mode, respectively. They are almost independent of the concentration in the solution. We further found from the low-frequency differential Kerr spectra of the solutions with neat CCl(4) that the intermolecular motion in the low frequency region below 20 cm(-1) was less active in the case of 7-azaindole/CCl(4) than in the case of 1-benzofuran/CCl(4). The slow orientational relaxation time in 7-azaindole/CCl(4) is ~3.5 times that in 1-benzofuran/CCl(4) because of the nature of the dimerization of 7-azaindole.  相似文献   

11.
To determine whether the addition of a methylene unit in the side chain of the Asp or Arg residue in alpha-human atrial natriuretic peptide (alpha-hANP) influences its biological activity, analogs of alpha-hANP, [Glu13]-alpha-hANP (7-28) (1), [Aad13]-alpha-hANP (7-28) (2), and [Harn]-alpha-hANP(7-28) (where n is any possible combination of 11, 14 and 27) (3-9), where the original Asp or Arg residue was replaced by a homo-amino acid, were synthesized by the solid-phase synthesis method. All the analogs were evaluated for their receptor binding, cyclic guanosine monophosphate (cGMP) accumulation activity in rat vascular smooth muscle cells (VSMC), and for vasorelaxant activity employing rat aorta. 1 and 2 were 0.9 and 0.03 times as potent as alpha-hANP (7-28), respectively, in binding. Har-containing analogs (3-9) were as potent as alpha-hANP (7-28) in binding. Among the Har-containing analogs, [Har11,14]-alpha-hANP (7-28) (6) and [Har11,27]-alpha-hANP (7-28) (7) were remarkably vasorelaxant active, being 4.2 and 5.3 times potent than alpha-hANP (7-28), respectively, in spite of relatively lower cGMP accumulation activity in the case of 7. The roles of the chargeable amino acid residues in biological activity are discussed.  相似文献   

12.
Phage T7 can be used as a biological UV dosimeter. Its reading is proportional to the inactivation rate expressed in HT7 units. To understand the influence of phage proteins on the formation of DNA UV photoproducts, cyclobutane pyrimidine dimers (CPD) and (6-4)photoproducts ((6-4)PD) were determined in T7 DNA exposed to UV radiation under different conditions: intraphage T7 DNA, isolated T7 DNA and heated phage. To investigate the effects of various wavelengths, seven different UV sources have been used. The CPD and (6-4)PD were determined by lesion-specific antibodies in an immunodot-blot assay. Both photoproducts were HT7 dose-dependently produced in all three objects by every irradiation source in the biologically relevant UV dose range (1-10 HT7). The CPD to (6-4)PD ratios increased with the increasing effective wavelength of the irradiation source and were similar in intraphage T7 DNA, isolated DNA and heated phage with all irradiation sources. However, a significant decrease in the yield of both photoproducts was detected in isolated T7 DNA and in heated phage compared to intraphage DNA, the decrease was dependent on the irradiation source. Both photoproducts were affected the same way in isolated T7 DNA and heated phage, respectively. The yield of CPD and (6-4)PD was similar in B, C-like and A conformational states of isolated T7 DNA, indicating that the conformational switch in the DNA is not the decisive factor in photoproduct formation. The most likely explanation for modulation of photoproduct frequency in intraphage T7 DNA is that the presence of bound phage proteins induces an alteration in DNA structure that can result in an increased rate of dimerization and (6-4)PD production of adjacent based in intraphage T7 DNA.  相似文献   

13.
In aqueous solution, bis(nucleoside) complexes formed by the reaction of cis-[Pt(NH3)2(H2O)2]2+ with an excess of either adenosine (ado) or a mixture of adenosine and guanosine (guo) undergo a slow N7--> N1 linkage isomerisation in the adenine moiety. The isomerisation probably involves the breaking and reformation of Pt-nucleoside bonds, thus favouring the more stable N1 binding mode of the adenine base. Dynamic processes due to the presence of adenosine in the platinum coordination sphere are slow on the NMR time scale. The N7 binding mode of PtII in cis-[Pt(NH3)2(ado-N7)2](ClO4)2. 3.5H2O was confirmed by X-ray crystal structure analysis. In both of the crystallographically independent cations, the PtII coordination sphere is almost ideally square planar, with typical Pt-N bond lengths and angles. The most significant difference between the two cations lies in the sugar conformation of the coordinated nucleosides. In one cation, both have an anti (-ap) conformation, whilst in the other cation one has an anti (-ap) conformation and the other a syn (+sc) conformation stabilised by a relatively strong H-bond. Substitution of the nucleoside(s) by thiourea follows an associative mechanism with only a negligible contribution by the solvent path. For symmetric complexes, the order of lability of different binding modes is ado-N1 相似文献   

14.
Electrodeposition of tin and tin alloys from electrolytes containing tin(II) and pyrophosphates is an important process in metal finishing, but the nature of the tin pyrophosphate complexes present in these solutions in various pH regions has remained unknown. Through solubility and pH studies, IR and (31)P and (119)Sn NMR spectroscopic investigations of solutions obtained by dissolving Sn(2)P(2)O(7) in equimolar quantities of either Na(4)P(2)O(7)·10H(2)O or K(4)P(2)O(7) the formation of anionic 1:1 complexes {[Sn(P(2)O(7))]}(n)(2n-) has now been verified and the molecular structures of the monomer (n = 1) and the dimer (n = 2) have been calculated by density functional theory (DFT) methods. Whereas the alkali pyrophosphates Na/K(4)P(2)O(7) give strongly alkaline aqueous solutions (pH ~13), because of partial protonation of the [P(2)O(7)](4-) anion, the [Sn(P(2)O(7))](2-) anion is not protonated and the solutions of Na/K(2)[Sn(P(2)O(7))] are almost neutral (pH ~8). The monomeric dianion appears to have a ground state with C(2v) symmetry with the Sn atom in a square pyramidal coordination and the lone pair of electrons in the apical position, while the dimer approaches C(2) symmetry with the Sn atoms in a rhombic pyramidal coordination, also with a sterically active lone pair. A comparison of experimental and calculated IR details favors the monomer as the most abundant species in solution. With an excess of pyrophosphate, 3:2 and 2:1 complexes (P(2)O(7)):(Sn) are first formed, which, in the presence of more pyrophosphate, undergo rapid ligand exchange on the NMR time scale. The structure of the 2:1 complex [Sn(P(2)O(7))(2)](6-) was calculated to have a pyramidal complexation by two 1,5-chelating pyrophosphate ligands. Neutralization of these alkaline solutions by sulfuric or sulfonic acids (H(2)SO(4), MeSO(3)H), as also practiced in electroplating, appears to afford the tin(II) hydrogen pyrophosphates [Sn(P(2)O(7)H)](-) and [Sn(H(2)P(2)O(7))](0). The molecular structures of the mononuclear model units have also been calculated and were shown to have an unsymmetrical complexation and to feature trigonal pyramidal (pseudotetrahedral) coordination. NMR observations have shown that, contrary to the results obtained for Sn(II) compounds, Sn(IV) as present in K(2)SnO(3) or its hydrated form (K(2)Sn(OH)(6)) does not form a pyrophosphate complex in aqueous solution near pH 7. There is also no interference of sulfite.  相似文献   

15.
The hydrogen storage properties of Li(7)VN(4) and Li(7)MnN(4) were investigated both by experiment and by density functional theory calculations. Li(7)VN(4) did not sorb hydrogen under our experimental conditions. Li(7)MnN(4) was observed to sorb 7 hydrogen atoms through the formation of LiH, Mn(4)N, and ammonia gas. An applied pressurized mixture of H(2)/Ar and H(2)/N(2) gases was helpful to mitigate the release of NH(3) but could not prevent its formation. The introduction of N(2) also caused weight gain of the sample by re-nitriding the absorbed products LiH and Mn(4)N, which correlated with the presence of Li(2)NH, LiNH(2), and Mn(2)N detected by X-ray diffraction. While our observed results for Li(7)VN(4) and Li(7)MnN(4) differ in detail, they are in overall qualitative agreement with our theoretical work, which strongly suggests that both compounds are unlikely to form quaternary hydrides.  相似文献   

16.
The classification of absorption bands in the acene series (, p, β-bands) was first based on the annellation effect and later on the polarization of the bands with regard to the molecular axes (Lb,La,Bb,Ba-bands). Both give the same result since annelation axes and molecular axes coincide. This is not so in the pyrene series. Annellation axes and molecular axes are different and it is shown that the classification of bands can be based only on the annellation effects. Moreover, the electronic asymmetry of the pyrene system is demonstrated by a striking asymmetric annellation effect. A number of higher annellated pyrenes have been synthesized:

1·-benzonaphtho-(2″·3″ :6·7)-pyrene, dinaphto-(2'·3 :1·2)-(2″·3″:6·7)-pyrene, 1·14,4·5-dibenzo-pentacene, 5·,15·16-dibenzohexacene, 6·7,16·17-dibenzoheptacene, 1·16,4·5-dibenzohexacene and 7·8,17·18-dibenzo-octacene.  相似文献   


17.
A new solid state organometallic route to embedded nanoparticle-containing inorganic materials is shown, through pyrolysis of metal-containing derivatives of cyclotriphosphazenes. Pyrolysis in air and at 800 °C of new molecular precursors gives individual single-crystal nanoparticles of SiP(2)O(7), TiO(2), P(4)O(7,) WP(2)O(7) and SiO(2), depending on the precursor used. High resolution transmission electron microscopy investigations reveal, in most cases, perfect single crystals of metal oxides and the first nanostructures of negative thermal expansion metal phosphates with diameters in the range 2-6 nm for all products. While all nanoparticles are new by this method, WP(2)O(7) and SiP(2)O(7) nanoparticles are reported for the first time. In situ recrystallization formation of nanocrystals of SiP(2)O(7) was also observed due to electron beam induced reactions during measurements of the nanoparticulate pyrolytic products SiO(2) and P(4)O(7). The possible mechanism for the formation of the nanoparticles at much lower temperatures than their bulk counterparts in both cases is discussed. Degrees of stabilization from the formation of P(4)O(7) affects the nanocrystalline products: nanoparticles are observed for WP(2)O(7), with coalescing crystallization occurring for the amorphous host in which SiP(2)O(7) crystals form as a solid within a solid. The approach allows the simple formation of multimetallic, monometallic, metal-oxide and metal phosphate nanocrystals embedded in an amorphous dielectric. The method and can be extended to nearly any metal capable of successful coordination as an organometallic to allow embedded nanoparticle layers and features to be deposited or written on surfaces for application as high mobility pyrophosphate lithium-ion cathode materials, catalysis and nanocrystal embedded dielectric layers.  相似文献   

18.
Metabolic studies of ipriflavone (TC-80) in rats by gas-liquid chromatography-mass spectrometry led to the characterization of the following metabolites: the parent compound, 7-hydroxy-3-phenyl-4H-1-benzopyran-4-one, 7-hydroxy-3-(4-hydroxyphenyl)-4H-1-benzopyran-4-one, 3-(4-hydroxyphenyl)-7-isopropoxy-4H-1-benzopyran-4-one, 2-(3-phenyl-4-oxo-4H-1-benzopyran-7-yl)oxypropionic acid, 2-[3-(4-hydroxyphenyl)-4-oxo-4H-1-benzopyran-7-yl]oxypropionic acid and 2-[3-(3-hydroxyphenyl)-4-oxo-4H-1-benzopyran-7-yl]oxypropionic acid. From the metabolites identified, TC-80 was shown to be metabolized primarily by oxidation. In vitro study using tissue slices of rats indicated that the above metabolic changes occurred exclusively in the liver. It was also demonstrated that the compound did not undergo metabolic conversion by gut flora of rats.  相似文献   

19.
Biofortification of pulse crops with Zn and Fe is a viable approach to combat their widespread deficiencies in humans. Lentil (Lens culinaris Medik.) is a widely consumed edible crop possessing a high level of Zn and Fe micronutrients. Thus, the present study was conducted to examine the influence of foliar application of Zn and Fe on productivity, concentration, uptake and the economics of lentil cultivation (LL 931). For this, different treatment combinations of ZnSO4·7H2O (0.5%) and FeSO4·7H2O (0.5%), along with the recommended dose of fertilizer (RDF), were applied to the lentil. The results of study reported that the combined foliar application of ZnSO4·7H2O (0.5%) + FeSO4·7H2O (0.5%) at pre-flowering (S1) and pod formation (S2) stages was most effective in enhancing grain and straw yield, Zn and Fe concentration, and uptake. However, the outcome of this treatment was statistically on par with the results obtained under the treatment ZnSO4·7H2O (0.5%) + FeSO4·7H2O (0.5%) at S1 stage. A single spray of ZnSO4·7H2O (0.5%) + FeSO4·7H2O (0.5%) at S1 stage enhanced the grain and straw yield up to 39.6% and 51.8%, respectively. Similarly, Zn and Fe concentrations showed enhancement in grain (10.9% and 20.4%, respectively) and straw (27.5% and 27.6% respectively) of the lentil. The increase in Zn and Fe uptake by grain was 54.8% and 68.0%, respectively, whereas uptake by straw was 93.6% and 93.7%, respectively. Also the benefit:cost was the highest (1.96) with application of ZnSO4·7H2O (0.5%) + FeSO4·7H2O (0.5%) at S1 stage. Conclusively, the combined use of ZnSO4·7H2O (0.5%) + FeSO4·7H2O (0.5%) at S1 stage can contribute significantly towards yield, Zn and Fe concentration, as well as uptake and the economic returns of lentil to remediate the Zn and Fe deficiency.  相似文献   

20.
6-Cyano-7-aminoquinoline (6CN−7AQ ) and 3-cyano-7-aminoquinoline ( 3CN−7AQ ) were synthesized and found to exhibit intense emission with quantum yield as high as 63 % and 85 %, respectively, in water. Conversely, their derivatives 6-cyano-7-azidoquinoline (6CN−7N3Q ) and 3-cyano-7-azidoquinoline ( 3CN−7N3Q ) show virtually no emission, which makes them suitable to be used as recognition agents in azide reactions based on fluorescence recovery. Moreover, conjugation of 6CN−7AQ with a hydrophobic biomembrane-penetration peptide PFVYLI renders a nearly non-emissive 6CN−7AQ-PFVYLI composite, which can be digested by proteinase K, recovering the highly emissive 6CN−7AQ with ∼200-fold enhancement. The result provides an effective early confirmation for RT-qPCR in viral detection.  相似文献   

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