Experimental and Theoretical Study of an Intramolecular CF3‐Group Shift in the Reactions of α‐Bromoenones with 1,2‐Diamines

The reactions of trifluoromethylated 2‐bromoenones and N,N′‐dialkyl‐1,2‐diamines have been studied. Depending on the structures of the starting compounds, the formation of 2‐trifluoroacetylpiperazine or 3‐trifluoromethylpiperazine‐2‐ones was observed. The mechanism of the reaction is discussed in terms of multistep processes involving sequential substitution of bromine in the starting α‐bromoenones and intramolecular cyclization of the captodative aminoenones as key intermediates to form the target heterocycles. The results of theoretical calculations are in perfect agreement with the experimental data. The unique role of the trifluoromethyl group in this reaction is demonstrated.     

气相色谱-质谱法测定甘蔗中除草剂残留量

提出了采用QuEChERS法提取净化,气相色谱-质谱法同时测定甘蔗中除草剂莠去津、乙草胺和莠灭净的残留量。采用DB-5MS毛细管柱分离,电子轰击离子源选择离子检测模式进行质谱测定。莠去津、乙草胺和莠灭净的检出限(3S/N)分别为0.001,0.002,0.001mg.kg-1。在3个浓度水平上对方法的回收率作了测定,测得回收率在88.0%～108.0%,相对标准偏差(n=6)在1.1%～6.9%之间。     

Hydrophobic Modification of Poly(Ethylene Terephthalate) with Epoxy-Modified Polysiloxane by Reactive Extrusion

Hydrophobic poly(ethylene terephthalate) (PET) was prepared by reactive blending of PET with double epoxy groups modified polysiloxane (diepsi) or multiepoxy groups modified polysiloxane (multiepsi). The structure of the modified PET was characterized by ¹H NMR and intrinsic viscosity. The grafted ratio of diepsi and multiepsi was 1.3 and 0.03 wt%, respectively. With the introduction of diepsi and multiepsi to PET, the water contact angle of modified PET increased from 73° to a maximum of 106°, showing the good hydrophobicity of the modified PET. The samples of modified PET were washed with different solvents and their water contact angles did not significantly decrease, indicating good durability of the hydrophobicity. Moreover, the films of modified PET prepared by solution casting (phenol and 1, 1, 2, 2-tetrachloroethane mixed solution) showed excellent hydrophobicity with the contact angle 151°. Scanning electron microscopy images showed the surface of the modified PET films to be rougher than those of unmodified PET because the introduction of polysiloxane to PET resulted in phase separation during the solvent evaporation process.     

Deuterium isotopic effect in 13C-N.M.R. spectra

We obtain the grand potential and the associated distribution functions for a system of hard rods on a line of finite length. These functions are shown to be related to those of a semi-infinite system bounded by one hard wall. It follows that the contact values of the density and distribution functions at the walls of the finite system are related to those at the wall of the semi-infinite system, and that the force on the walls is the density at contact. We obtain also the density and distribution functions for a system with repeating boundary conditions, which are also expressible in terms of those of the finite and semi-infinite systems.     

Liquid–liquid extraction of neodymium (III) and europium (III) using synergic mixture of furosemide and tribenzylamine in benzyl alcohol

The extraction behavior of Nd(III) and Eu(III) with 0.05 mol dm⁻³ furosemide in benzyl alcohol as single acidic extractant and then with equimolar (0.05 mol dm⁻³) synergic mixture of furosemide as acidic extractant and tribenzylamine as neutral donor in benzyl alcohol has been studied from aqueous solutions of pH 1 to 6. The effect of various parameters and of various cations and anions on the extraction of these metal ions was investigated. The composition of the extracted adducts was determined by slope analysis method that came out to be [(M(FS)₂)⁺ (CH₃COO)⁻] and [M(FS)₃·3TBA] where M = Nd(III) and Eu(III).

     

真空、低能离子注入对人宫颈癌（HeLa）细胞中 p53及c-fos mRNA的表达影响

在具有高效护水功能石蜡油的保护下进行了人宫颈癌细胞(HeLa细胞)的低能离子注入及真空处理, 用荧光定量PCR的方法分别研究了真空和30 keV N+的不同注入剂量下, 细胞中p53基因和c-fos基因的mRNA表达变化。 结果表明, 上述两个基因的表达与真空及低能离子注入之间存在着剂量关系。     

Heteroorganic betaines

The structures of 6,6-dimethyl-6-silafulvene C₅H₄SiMe₂ (3), its donor-acceptor complex with ammonia. C₅H₄SiMe₂·NH₃, dimethylfulvene, a number of cyclopentadienylides, methylenetrimethylphosphorane (6), and silicon-containing organophosphorus betaine⁻C₅H₄SiMe₂CH₂PMe₃ ⁺ (13), the product of nucleophilic addition of6 to3, were calculated using the density functional approach. For compound13, the potential energy minimum corresponds to the conformation withgauche-arrangement of the cyclopentadienyl anionie and trimethylphosphonium cationic centers and a C−Si−C−P dihedral angle of 30.5°, which is due to the Coulomb attraction between these centers. According to calculations, betaine13 is rather stable toward decomposition into3 and6 (ΔH ^o=42 kcal mol⁻¹, ΔG ^Δ=30 kcal mol⁻¹). The main channel of thermal decomposition of compound13 involves an intramolecular nucleophilic substitution, which proceeds with elimination of trimethylphosphine and results in 1,1-dimethyl-1-silaspiro[2,4]hepta-4,6-diene, which then undergoes a ready and irreversible isomerization into 6,6-dimethyl-6-silabicyclo[3.2.0]hepta-1,3-diene owing to the [1.5]-sigmatropic shift of the C−Si bond. For Part 4, see Ref. 1. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1850–1857, November, 2000.     

类锂铝离子能级结构及光谱线性质的理论计算

用Ｈａｒｔｒｃｅ－Ｆｏｃｋ－Ｒｅｌａｔｉｖｉｓｔｉｃ（ＨＦＲ）自洽场方法,计算类锂铝离子１ｓ＾２ｎｌ（ｎ＝２～７,ｌ＝０～５）,１ｓｎｌｎ’ｌ’（ｎ,ｎ’＝２～３,ｌ,ｌ’＝０～２）各能级值,电偶极跃迁谱线的光谱线性质（波长、振子强度和跃迁几率）,其波长计算值和现有文献结果符合得较好。特别是实验中已观察到的软Ｘ射线激光跃迁（３ｄ－４ｆ,３ｄ－５ｆ）的波长值与我们的计算值符合得也很好。     

Reactions of carbonylmetallate anions with 1-haloalkynes

The main regularities of the reactions of 1-haloalkynes RC≡CX with carbonylmetallate anions [(η⁵-C₅R′₅)(CO)₃M]⁻ (R′ = H (1–3),, M=Cr (1), M=Mo (2), or M=W (3); R′ =Me (4–6), M=Cr (4), M=Mo (5), or M=W (6) were revealed. It was established that the first stage of the reactions of anions1–6 with bromo- or iodoalkynes RC≡CX (X=Br or I) involved the transfer of the halogen atom from the sp-hybridized carbon atom to the transition metal atom to form carbonyl halides [(η⁵-C₅R′₅)(CO)₃MX. To the contrary, the reactions of anions1–6 with chloroalkynes RC≡CCl proceeded selectively as a nucleophilic substitution at the unsaturated carbon atom, the reaction rate being governed by the nucleophilicity of the carbonylmetallate anions and the electron-withdrawing ability of the R group. These reaction paths are consistent with the structures of the lowest unoccupied molecular orbitals (LUMO) in the PhC≡CX molecules (X=Cl, Br, or I) calculated by the MNDO/PM3 method. In the case of the reactions of 1-chloroheptyne-1 C1C≡CC₅H₁₁ ⁿ, anions1–3 appeared to be insufficiently nucleophilic, but these reactions can be performed as cross-coupling of the carbonylmetallate anions with chloroalkynes catalyzed by palladium complexes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1176–1184, June, 1999.     

Damping Effects on the. Reflection of the Metallic Superlattice for Soft X-Rays and Extreme Ultraviolet

Based on the hydrodynamic model theory and the transfer-matrix-method, we have reexamined the reflection properties by taking account of damping effects to the system of the metallic superlattice for the S-polarized soft X-rays and extreme ultraviolet. Fot the normal incidence, we find that the reflection intensity spectxm will decline monotonously with the increasing of the retardation, but for the regions of the higher frequencies and the smaller grazing angles, the damping effects could be neglected.