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51.
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Oligonucleotides containing 7‐deaza‐2′‐deoxyinosine derivatives bearing 7‐halogen substituents or 7‐alkynyl groups were prepared. For this, the phosphoramidites 2b – 2g containing 7‐substituted 7‐deaza‐2′‐deoxyinosine analogues 1b – 1g were synthesized (Scheme 2). Hybridization experiments with modified oligonucleotides demonstrate that all 2′‐deoxyinosine derivatives show ambiguous base pairing, as 2′‐deoxyinosine does. The duplex stability decreases in the order Cd>Ad>Td>Gd when 2b – 2g pair with these canonical nucleosides (Table 6). The self‐complementary duplexes 5′‐d(F7c7I‐C)6, d(Br7c7I‐C)6, and d(I7c7I‐C)6 are more stable than the parent duplex d(c7I‐C)6 (Table 7). An oligonucleotide containing the octa‐1,7‐diyn‐1‐yl derivative 1g , i.e., 27 , was functionalized with the nonfluorescent 3‐azido‐7‐hydroxycoumarin ( 28 ) by the Huisgen–Sharpless–Meldal cycloaddition ‘click’ reaction to afford the highly fluorescent oligonucleotide conjugate 29 (Scheme 3). Consequently, oligonucleotides incorporating the derivative 1g bearing a terminal C?C bond show a number of favorable properties: i) it is possible to activate them by labeling with reporter molecules employing the ‘click’ chemistry. ii) Space demanding residues introduced in the 7‐position of the 7‐deazapurine base does not interfere with duplex structure and stability (Table 8). iii) The ambiguous pairing character of the nucleobase makes them universal probes for numerous applications in oligonucleotide chemistry, molecular biology, and nanobiotechnology. 相似文献
54.
Indu Negi Bimaldeep Singh Amanpreet Singh Mahmi Dr. Purshotam Sharma 《Chemphyschem》2023,24(5):e202200714
Expansion of the genetic alphabet is an ambitious goal. A recent breakthrough has led to the eight-base (hachimoji) genetics having canonical and unnatural bases. However, very little is known on the molecular-level features that facilitate the candidature of unnatural bases as genetic alphabets. Here we amalgamated DFT calculations and MD simulations to analyse the properties of the constituents of hachimoji DNA and RNA. DFT reveals the dominant syn conformation for isolated unnatural deoxyribonucleosides and at the 5′-end of oligonucleotides, although an anti/syn mixture is predicted at the nonterminal and 3′-terminal positions. However, isolated ribonucleotides prefer an anti/syn mixture, but mostly prefer anti conformation at the nonterminal positions. Further, the canonical base pairing combinations reveals significant strength, which may facilitate replication of hachimoji DNA. We also identify noncanonical base pairs that can better tolerate the substitution of unnatural pairs in RNA. Stacking strengths of 51 dimers reveals higher average stacking stabilization of dimers of hachimoji bases than canonical bases, which provides clues for choosing energetically stable sequences. A total of 14.4 μs MD simulations reveal the influence of solvent on the properties of hachimoji oligonucleotides and point to the likely fidelity of replication of hachimoji DNA. Our results pinpoint the features that explain the experimentally observed stability of hachimoji DNA. 相似文献
55.
Oishi Tomohiro 《原子核物理评论》2016,33(2):203-206
We calculate the two-proton decay width of the 6Be nucleus employing the schematic densitydependent contact potential for the proton-proton pairing interaction. The decay width is calculated with a time-dependent method, in which the two-proton emission is described as a time-evolution of a threebody meta-stable state. Model-dependence of the two-proton decay width has been shown by comparing the results obtained with the two different pairing models, schematic density-dependent contact and Minnesota interactions, which have zero and finite ranges, respectively. 相似文献
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Arakelov and Faltings developed an admissible theory on regulararithmetic surfaces by using Arakelov canonical volume formson the associated Riemann surfaces. Such volume forms are inducedfrom the associated Kähler forms of the flat metric onthe corresponding Jacobians. So this admissible theory is inthe nature of Euclidean geometry, and hence is not quite compatiblewith the moduli theory of Riemann surfaces. In this paper, wedevelop a general admissible theory for arithmetic surfaces(associated with stable curves) with respect to any volume form.In particular, we have a theory of arithmetic surfaces in thenature of hyperbolic geometry by using hyperbolic volume formson the associated Riemann surfaces. Our theory is proved tobe useful as well: we have a very natural Weil function on themoduli space of Riemann surfaces, and show that in order tosolve the arithmetic Bogomolov-Miyaoka-Yau inequality, it issufficient to give an estimation for Petersson norms of somemodular forms. 1991 Mathematics Subject Classification: 11G30,11G99, 14H15, 53C07, 58A99. 相似文献
58.
Valeriy V. Bezrodnyi Sofia E. Mikhtaniuk Oleg V. Shavykin Igor M. Neelov Nadezhda N. Sheveleva Denis A. Markelov 《Molecules (Basel, Switzerland)》2021,26(21)
Novel peptide dendrimer with Lys-2His repeating units was recently synthesized, studied by NMR (Molecules, 2019, 24, 2481) and tested as a nanocontainer for siRNA delivery (Int. J. Mol. Sci., 2020, 21, 3138). Histidine amino acid residues were inserted in the spacers of this dendrimer. Increase of their charge with a pH decrease turns a surface-charged dendrimer into a volume-charged one and should change all properties. In this paper, the molecular dynamics simulation method was applied to compare the properties of the dendrimer in water with explicit counterions at two different pHs (at normal pH with neutral histidines and at low pH with fully protonated histidines) in a wide interval of temperatures. We obtained that the dendrimer at low pH has essentially larger size and size fluctuations. The electrostatic properties of the dendrimers are different but they are in good agreement with the theoretical soft sphere model and practically do not depend on temperature. We have shown that the effect of pairing of side imidazole groups is much stronger in the dendrimer with neutral histidines than in the dendrimer with protonated histidines. We also demonstrated that the capacity of a nanocontainer based on this dendrimer with protonated histidines is significantly larger than that of a nanocontainer with neutral histidines. 相似文献
59.
分析了20 < A < 190范围内丰中子核β衰变的实验数据,根据半衰期随质子数、中子数以及衰变能变化所呈现的壳效应和对效应等特点,提出了一种有效估算丰中子核β衰变寿命的公式。新的计算公式形式简单包含了较少的参数、计算量小。用该公式能较为准确地再现丰中子核的β衰变半衰期。用RIKEN最新测量丰中子核半衰期检验了该公式的外推能力,本工作可以为r-过程研究提供可靠的输入数据。Experimental data of the β--decay half-lives for the nuclei with atomic number between 20 and 190 are investigated. We have systematically studied the shell effects and pairing effects on β--decay half-lives versus the decay energy Q and nucleon numbers (Z, N). An empirical formula has been proposed to calculate the β--decay half-lives of neutron-rich nuclei. The empirical formula is simple and has relatively few parameters. Experimental β--decay half-lives of the neutron-rich nuclei are well reproduced by the new formula. In addition, the extrapolating capacity of this formula has been checked with the very recent experimental data from RIKEN. The predicted half-lives for r-process relevant nuclei with the current formula can be served as the reliable input of r-process model calculations. 相似文献
60.
采用基于推转壳模型的粒子数守恒方法对105Cd 和106Cd 中的反磁转动带进行了研究,在计算当中,粒子数严格守恒,并且堵塞效应也是严格考虑的。计算结果很好地再现了实验上观测到的I-Ω 关系、转动惯量以及约化跃迁几率B(E2)。通过检验双剪角,即两个质子空穴角动量的合拢,对反磁转动中的双剪刀机制进行了分析。研究表明剪刀角的合拢非常敏感地依赖于对关联。The antimagnetic rotation bands in 105;106Cd are investigated by the cranked shell model with pairing correlations treated by a particle-number conserving method, in which the blocking effects are taken into account exactly. The experimental moments of inertia, I-Ω relation and the reduced B(E2) transition probabilities are well reproduced. The two-shears-like mechanism for the antimagnetic rotation is investigated by examining the shears angle, i.e., the closing of the two proton hole angular momenta. The sensitive dependence of the shears angle on the nuclear pairing correlations is revealed. 相似文献