Approaches to open fullerenes: a 1,2,3,4,5,6-hexaadduct of C60

Complete saturation of a single six-membered ring on fullerene C60 has been achieved. The critical step in this first synthesis of a fully characterized 1,2,3,4,5,6-hexaadduct consisted of a remarkable double 5-exo-trig addition of alkoxyl radicals promoted by lead tetraacetate. Two possible opening pathways ([2 + 2 + 2] retrocycloadditions) for the newly synthesized compound were explored using quantum mechanical calculations. We found that the oxa bridges in the hexaadduct prevent ring opening through the retro[2 + 2 + 2] mechanism due to the high activation barrier and endothermicity of the reaction.     

Application of LC/MS and ICP/MS for establishing the fingerprint spectrum of the traditional Chinese medicinal preparation Gan-Lu-Yin

We developed a method to analyze the fingerprint spectrum qualitatively and quantitatively for the traditional Chinese herbal medicinal preparation Gan-Lu-Yin with HPLC combined with photodiode array detection, and MS, and to identify the preparation's 14 main components including baicalin, baicalein, oroxylin A-7-O-glucuronide, wogonin-7-O-glucuronide, wogonin, and oroxylin A in Radix Scutellariae; naringin and neohesperidin in Aurantii fructus; liquiritigenin, liquiritin, and glycyrrhizic acid in Radix Glycyrrhizae. In LC/UV assay, a Cosmosil 5C18-MS-II column was used as the stationary phase, and a gradient of potassium dihydrogen phosphate, ACN, and water as the elute solution. The UV detection wavelengths were 250 and 280 nm. In LC/MS assay, a gradient of phosphoric acid, ACN, and water was used as the elute solution, and electrospray positive ion mode ((+)-ESI) as the analytic mode. In order to explore the distribution of trace metal elements effectively in Gan-Lu-Yin, a microwave digestion method was used for sample treatment, and an inductively coupled plasma MS assay was used to analyze fingerprint spectra of the inorganic metals in Gan-Lu-Yin. Combined with fingerprint spectra of organic compounds by LC/UV and LC/MS, it was expected to provide effective quality control in the production of Gan-Lu-Yin.     

Photophysical properties of a 1,2,3,4,5,6-hexasubstituted fullerene derivative

The photophysical properties of a novel 1,2,3,4,5,6-hexasubstituted fullerene derivative (1) are examined in this study. In addition to the ground state absorption spectrum of 1, we report its triplet-triplet absorption spectrum and molar extinction coefficient (Deltae(T-T)), as well as the triplet quantum yield (PhiT), lifetime (tauT), and energy (ET). The saturation of a single six-member ring on the fullerene cage results in significant changes in the triplet state properties as compared to that of pristine C60. The triplet-triplet absorption spectrum shows a hypsochromic shift in long wavelength absorption, and both the triplet state lifetime and the triplet quantum yield are decreased. The triplet energy was found to be similar to that of C60. In addition, the quantum yield (PHI(delta)) of singlet oxygen generated by 1 was calculated and is found to be significantly less than in the case of C60.     

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用线圈电流控制非平衡磁场,用汤森放电击穿形成深度自触发放电,用磁阱捕获放电形成的二次电子和导致漂移电流,形成了高功率非平衡磁控溅射放电。采用偏压为-100V相对磁控靶放置的圆形平面电极收集饱和离子电流;在距离磁控靶14cm的位置由Langmuir探针测量浮置电位;示波器测量磁控靶的脉冲电压、电流、浮置电位和饱和离子电流信号。装置的放电脉冲功率达到0.9MW,脉冲频率最大值为40Hz左右,空间电荷限制条件是控制电子电流和离子电流的主要机制。     

Image watermarking by using phase retrieval algorithm in gyrator transform domain

We propose an image watermarking scheme based on the phase retrieval algorithm in gyrator domain. The watermark is converted into a noise-like image by Arnold transform. The scrambled image is regarded as the amplitude of gyrator spectrum. The Gerchberg-Saxton algorithm is employed to obtain the unknown phase function in gyrator pair, in which the host image is the amplitude of input function. The phase information and the parameters of the two transforms serve as the key of watermarking algorithm. The numerical simulation has demonstrated the performance of the proposed algorithm.     

Elastic heterogeneity in metallic glasses

When a stress is applied on a metallic glass it deforms following Hook's law. Therefore it may appear obvious that a metallic glass deforms elastically. Using x-ray diffraction and anisotropic pair-density function analysis we show that only about 3/4 in volume fraction of metallic glasses deforms elastically, whereas the rest of the volume is anelastic and in the experimental time scale deform without resistance. We suggest that this anelastic portion represents residual liquidity in the glassy state. Many theories, such as the free-volume theory, assume the density of defects in the glassy state to be of the order of 1%, but this result shows that it is as much as a quarter.     

Higher derivations of ore extensions

Let R be a prime ring and δ a derivation of R. Divided powers $ D_n ^{\underline{\underline {def.}} } \tfrac{1} {{n!}}\tfrac{{d^n }} {{dx^n }} $ D_n ^{\underline{\underline {def.}} } \tfrac{1} {{n!}}\tfrac{{d^n }} {{dx^n }} of ordinary differentiation d/dx form Hasse-Schmidt higher derivations of the Ore extension (skew polynomial ring) R[x; δ]. They have been used crucially but implicitly in the investigation of R[x; δ]. Our aim is to explore this notion. The following is proved among others: Let Q be the left Martindale quotient ring of R. It is shown that $ S^{\underline{\underline {def.}} } Q[x;\delta ] $ S^{\underline{\underline {def.}} } Q[x;\delta ] is a quasi-injective (R, R)-module and that any (R,R)-bimodule endomorphism of S can be uniquely expressed in the form

Prime radicals of constants of algebraic derivations

Let R be a prime ring with extended centroid F and let δ be an F-algebraic continuous derivation of R with the associated inner derivation ad(b). Factorize the minimal polynomial μ(λ) of b over F into distinct irreducible factors ${\mu(\lambda)=\prod_i\pi_i(\lambda)^{n_i}}$ . Set ? to be the maximum of n _i . Let ${R^{(\delta)}{\mathop{=}\limits^{{\rm def.}}}\{x\in R\mid \delta(x)=0\}}$ be the subring of constants of δ on R. Denote the prime radical of a ring A by ${{\mathcal{P}}(A)}$ . It is shown among other things that $${\mathcal{P}}(R^{(\delta)})^{2^\ell-1}=0\quad\text{and}\quad{\mathcal{P}}(R^{(\delta)})=R^{(\delta)}\cap {\mathcal{P}}(C_R(b))$$ .     

Switch of electronic reactivity in fullerene C60: activation of three trans-4 positions via temporary saturation of the cis-1 positions

[Structure: see text] The regioselective functionalization of C60 with a trans-4,trans-4,trans-4 trisaddition pattern is not feasible directly. We have found an indirect approach taking advantage of the modified electronic reactivity of cis-1 bisadducts. The cis-1 addition pattern electronically activates three trans-4 C=C bonds on the opposite hemisphere of C60, allowing further highly regioselective additions at these positions. Thermal removal of the cis-1 blocking unit results in a trans-4,trans-4,trans-4 trisadduct with C3v symmetry.