Ab initio study of the ground state and conformational stability of peroxyacetyl nitrate in internal rotation about the peroxide bond

The molecular and electronic structure of the ground state of peroxyacetyl nitrate (PAN) was calculated by the unrestricted Hartree-Fock-Roothaan method with the use of the standard 3–21G and 6–31G basis set. The potential curve of the internal rotation about the peroxide bond of PAN was calculated with the 6–31G basis set. The curve contains two maxima. The ground state of PAN is characterized by a structure in which groups of atoms adjacent to the peroxide bond lie in planes that are perpendicular to each other (the dihedral angle ϱ(COON) is 89.9°). The calculated barriers to rotation are 19.6 and 66.8 kJ mol⁻¹. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 600–604, April, 1998.     

Optical rotation inversion of porphyrin-DNA complexes

A porphyrin-DNA complex in which helical porphyrin assemblies were stacked as π-stacked aggregates on a DNA scaffold was found. The complex indicates the inversions of optical rotation by only the control of ionic equilibrium without any structural changes of DNA scaffold.     

S1←S0 Vibronic spectra and the structure of acetyl fluoride-h3 and acetyl fluoride-d3 molecules

UV absorption spectra of acetyl fluoride-h₃ and -d₃ (CH₃COF and CD₃COF) molecules in the region of S₁S₀ electronic transitions are investigated. The origins (0⁰ ₀ or 14^0± ₀) of these transitions are observed at 39912 and 39904 cm^–1, respectively, and some of the fundamental frequencies of these molecules in the s₀ and S₁ states are determined. In particular, the systems of torsion and inversion (out-of-plane C=O vibrations) energy levels are studied. The geometric parameters of an acetyl fluoride-h₃ molecule in the S₁ state are estimated by the theoretical simulation of the rotational contours of the 0⁰ ₀ (14^0± ₀) band. These data are used to evaluate the potential barriers to internal rotation in the S₀ and S₁ states, which were found to be 360 and 560 cm^–1 for acetyl fluoride-h₃ and 380 and 770 cm^–1 for acetyl fluoride-d₃, respectively, as well as the potential barriers to inversion in the S₁ states, which were found to be 2090 and 2370 cm^–1 for acetyl fluoride-h₃ and acetyl fluoride-d₃, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1957–1964, November, 1994.In conclusion, the authors would like to acknowledge T. S. Kuznetsova for the synthesis and purification of the AF samples.The research presented here was supported in part by the International Science Foundation under grant No. MJ 1000.     

The effect of low concentrations of a polyatomic gas in argon on erosion on copper cathodes in a magnetically rotated arc

Experimental results are presented for electrode erosion on copper cathodes in magnetically rotated arcs in argon, dry air, nitrogen, ammonia, and carbon monoxide as well mixtures of the above with argon. Water-saturated argon was also used. Erosion rates were determined by weight loss after chemical cleaning, and the runs were sufficiently long (between 5 to 60 min) to represent steady-state operation. Arc currents of 100 A and gas pressures of 1.1 atm. were used. Pure argon gave the highest erosion rates and the lowest arc velocities. Small concentrations of any of the diatomic gases in argon greatly increased the arc velocity and decreased the erosion rates. The results suggest that erosion is primarily a thermal phenomenon but that the surface chemistry can greatly influence erosion rates by modifying arc behavior.     

旋转输液管动力稳定性理论分析北大核心CSCD

基于Lagrange原理和假设模态法建立了旋转输液管的动力学模型.通过降阶升维的方法求解系统的特征值问题,并分析了旋转输液管自由振动特性.得到了不同端部集中质量和转速下,系统特征值随流速升高的演变轨迹.揭示了临界流速随系统参数的变化规律.研究发现,内部流体的流动对旋转输液管动力学特性存在显著影响.在某些参数组合下,系统低阶模态能够形成不同形式的内共振关系.预示了旋转输液管模型蕴含丰富的动力学现象.     

“黑麦草-水稻”草田轮作系统的根际效应 Ⅱ.冬种黑麦草对土壤物理化学性状的影响

研究了冬种黑麦草对土壤物理化学性状的影响．结果表明,冬种黑麦草使土壤容质量下降９．４％,而对照区仅下降４．０％;冬种黑麦草使土壤有机质质量分数提高了６６％,而对照区降低了１４％;冬种黑麦草使土壤的全Ｎ,全Ｐ和有效Ｎ,有效Ｐ的质量分数分别提高了２６％,３２％,６７％和３３％,而对照区下降了１３％,４％,２０％和１３％;冬种黑麦草使土壤的全Ｋ和有效Ｋ质量分数提高了１４％和７８％,对照区也提高了１０％和１０％;种草区虽然土壤养分的增加与施肥有关,但有效Ｎ和Ｋ的增加显然还受到根际效应的影响,其证据是：在种草区,尽管土壤中的Ｎ通过收获黑麦草产生了较大的净输出（２８．０ｇ／ｍ２）,但土壤Ｎ含量仍然有不寻常的增加,说明可能存在着不明Ｎ源．２种养分有效含量的增幅比全量的增幅更大．从收获的黑麦草中发现土壤有Ｎ的净输出,可能是由于冬种黑麦草有不明来源的Ｎ素积累．     

核磁共振弛豫时间的测量

本文指出了在核磁共振实验中通常使用的通过测量信号宽度求横向弛豫时间的方法的局限性。介绍了以特殊的射频脉冲序列来测量横向弛豫时间的“自旋──回波”方法和测量纵向弛象时间的“倒置──恢复”方法．     

Scaling properties of ℤ k- 1 actions on the circle

We derive universal scaling properties for ^k–1 actions on the circle whose generators have rotation numbers algebraic of degreek. As fork=2 these properties can be explained for arbitraryk in terms of a renormalization group transformation. It has at least one trivial fixed point corresponding to an action whose generators are pure rotations. The spectrum of the linearized transformation in this fixed point is analyzed completely. The fixed point is hyperbolic with a (k–1)-dimensional unstable manifold. In the casek=2 the known results are therefore recovered.     

Controlled/“Living “Radical Polymerization of(-)-Menthyl Methacrylate

The atom transfer radical polymerization(ARP)of (-)-menthyl methacrylatc((-)-MnMA) mediated by CuCl/bipyridine and ethy1 2-bromopropionate or 1-phenylethyl bromide in THF system has been studied.The dependence of the specific rotation on molecular weight and the CD of Poly((-)-MnMA) thus obatined was investigated.