Thermodynamic molecular switch in sequence‐specific hydrophobic interactions

This communication will demonstrate the existence of a thermodynamic molecular switch in the pairwise, sequence‐specific hydrophobic interaction of Ile–Ile, Leu–Ile, Val–Leu, or Ala–Leu over the temperature range of 273–333 K reported by Nemethy and Scheraga in 1962. Based on Chun's development of the Planck–Benzinger methodology, the change in inherent chemical bond energy at 0 K, ΔH°(T₀), is 3.0 kcal mol^?1 for Ile–Ile, 2.4 for Leu–Ile, 1.8 for Val–Leu, and 1.2 kcal mol^?1 for Ala–Leu. The value of ΔH°(T₀) decreases as the length of the hydrophobic side chain decreases. It is clear that the strength and stability of the hydrophobic interaction is determined by the packing density of the side chains, with Ala–Leu being the most stable. At 〈T_m〉, the thermal agitation energy, $\int^{T}_{0}\Delta Cp^{\circ}(T)\,dT$, is about five times greater than ΔH°(T₀) in each case. Additionally, the thermal agitation energy for the same series, evaluated at 〈T_m〉, decreases in the same order, that is, as the length of the side chain decreases. This pairwise, sequence‐specific hydrophobic interaction is highly similar in its thermodynamic behavior to that of other biological systems, except that the negative Gibbs free energy change minimum at 〈T_s〉 occurs at a considerably higher temperature, 355 K compared to about 300 K. The melting temperature, 〈T_m〉, is also high, 470 K compared to 343 K in a biological system. The implication is that the negative Gibbs free energy minimum at a well‐defined 〈T_s〉 has it origin in the hydrophobic interactions, which are highly dependent on details of molecular structure. In addition to the four specific dipeptide interactions described, we have shown in our unpublished work the existence of a thermodynamic molecular switch in the interactions of 32 dipeptides wherein a change of sign in ΔCp°(T)_reaction leads to a true negative minimum in the Gibbs free energy of reaction, and hence, a maximum in the related K_eq. Indeed, all interacting biological systems that we have thus far examined using the Planck–Benzinger approach point to the universality of thermodynamic molecular switches. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

卟啉超分子化合物在分子器件中的应用

分子电子器件已成为近年来的一个研究热点，卟啉类化合物因为光敏性好、性能稳定、易于修饰等优点成为分子器件研究的理想模型化合物。本文着重介绍了它在分子器件中的最新应用进展。     

[Ru(phen)2dppz]2+二聚及对DNA键合性质的影响

研究发现, [Ru(phen)2dppz]2+表现出非常强的自聚合倾向, 并显著影响DNA的键合性质, 有关方面的研究应引起科研工作者的足够重视.     

电爆炸箔断路开关的理论和实验研究

 采用金属箔电爆炸过程的二维数值计算模型，对含电爆炸金属箔断路开关的电感储能脉冲功率调节系统进行了数值计算。以此为基础，研制出了一种低电感型的电爆炸箔断路开关，并以4μF/75kV脉冲电容器组作为初级能源，13Ω电阻作为负载进行实验研究。研究结果表明：在负载上可获得约250kV，脉宽大于400ns的脉冲电压。     

S-5N全固态重复频率脉冲发生器

 主要介绍S-5N的结构及测试实验结果。S-5N型全固态重复频率脉冲发生器是目前国际上同类源中峰值功率和平均功率均为最大的一台。随负载大小的变化，S-5N脉冲发生器的输出电压为400～600kV，输出电流2～3kA，输出脉冲半高宽40～50ns，单脉冲输出能量40～65J。 S-5N脉冲发生器在300Hz重复频率条件下可连续工作，500Hz重复频率条件下可连续工作3min，平均输出功率高达30kW。     

基于开关控制的兴趣实验设计

设计了开关控制实验,专门对常见的开关特点及使用进行探讨,根据开关特点搭建相应的控制电路,用近似于工程项目的形式锻炼学生对开关的灵活应用,激发了学生实验的兴趣和积极性.     

New designed DNA light switch Ruthenium complexes as DNA photocleavers and Topoisomerase I inhibitors

Two ruthenium complexes containing a new ligand phipz (phipz = 2‐(1,10‐phenanthroline)‐1H‐imidazo[4,5‐b]phenazine) were designed and synthesized. These complexes were found to inhibit the DNA supercoiled relaxation mediated by topoisomerase I (topo I), cleave DNA under irradiation and bind to calf thymus DNA through intercalative mode. Furthermore, complex 2 shows higher photocleavage activity, topo I inhibition activity and DNA affinity than complex 1 . Additionally, introduction of phenazine unit may be the reason that two complexes exhibit DNA ‘light switch’ behavior. The present work shows that two complexes might be potential as new DNA ‘light switches’, DNA photocleavers and topo I inhibitors.     

衰减振荡电流下火花电阻的光谱诊断

气体开关是脉冲功率系统的关键部件,开关的火花通道阻抗直接影响负载电压的陡度及其能量传输效率。提出一种光谱学诊断方法,通过对火花通道成像光谱的时空分辨测量,获得通道半径及电导率,从而计算时变的火花电阻。光谱测量结果表明,氮气间隙火花放电通道电子温度为2~3eV,通道电导率先增大后减小,最大值约16 000S,随着放电发展,火花通道电阻从绝缘状态快速跌落并趋于稳定值,时变趋势与电学计算结果基本吻合。3~100kPa范围内,随着气压增大,放电通道半径减小,火花通道电阻增大。