6-羟基-5,12-萘并萘醌及其CH3, C6H5取代衍生物的光致变色理论研究

用密度泛函理论的B3LYP/6-31G方法和从头算的CIS/6-31G方法分别研究了6-羟基-5,12-萘并萘醌及其CH₃, C₆H₅取代衍生物基态和激发态的异构化反应，.对反应势能面的研究发现, 在光异构化反应中化合物M21和M21、M31的基态和激发态虽然都可以构成四能级反应过程, 但由于M21异构化过程的活化能较高, 使其所构成的四能级反应难以进行, 这就从理论上解释了迁移基团为甲基的M21变色性能低于迁移基团为苯基的M31的实验结果. 此外用TD/B3LYP方法在溶剂存在下计算了上述化合物的紫外吸收光谱和荧光发射光谱, 计算所得到的光谱数据与实验值基本一致, 与光异构化反应的光激发条件相符合.     

Electronic properties of polyoxometalates: a DFT study of alpha/beta-[XM(12)O(40)](n-) relative stability (M=W, Mo and X a main group element)

Keggin heteropolyanions [XM(12)O(40)](n-) have various isomeric structures, alpha and beta being the most common. Conventionally, the alpha structure appears to be the most stable, but calculations carried out at the DFT level for X = P(V), Si(IV), Al(III), As(V), Ge(IV), and Ga(III) and M = W(VI) and Mo(VI) show that this stability depends on several factors, particularly on the nature of the heteroatom (X) and the total charge of the cluster. In this paper, we apply the clathrate model to the Keggin molecule to carry out a fragment-interaction study to elucidate when and why the traditional relative stability of various isomers can be inverted. The fully oxidized anions that have inverted the traditional stability trend in this series are [AlW(12)O(40)](5-) and [GaW(12)O(40)](5-), both of which contain a third-group heteroatom and an overall charge of -5. beta-isomers are always more easily reduced than alpha-isomers. This experimental observation suggests that reduction favors the stability of beta-isomers and one of the most important results of this study is that the alpha/beta inversion is achieved in most cases after the second reduction. The alpha- and beta-isomers may have different properties because the energy of the LUMO, a symmetry-adapted d(xy)-metal orbital, is different.     

Energetic ion bombardment of Ag surfaces by C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> and Ga<Superscript>+</Superscript> projectiles

The ion bombardment-induced release of particles from a metal surface is investigated using energetic fullerene cluster ions as projectiles. The total sputter yield as well as partial yields of neutral and charged monomers and clusters leaving the surface are measured and compared with corresponding data obtained with atomic projectile ions of similar impact kinetic energy. It is found that all yields are enhanced by about one order of magnitude under bombardment with the C60+ cluster projectiles compared with Ga+ ions. In contrast, the electronic excitation processes determining the secondary ion formation probability are unaffected. The kinetic energy spectra of sputtered particles exhibit characteristic differences which reflect the largely different nature of the sputtering process for both types of projectiles. In particular, it is found that under C60+ impact (1) the energy spectrum of sputtered atoms peaks at significantly lower kinetic energies than for Ga+ bombardment and (2) the velocity spectra of monomers and dimers are virtually identical, a finding which is in pronounced contrast to all published data obtained for atomic projectiles. The experimental findings are in reasonable agreement with recent molecular dynamics simulations.     

正交信号校正在正常成人血清1H NMR谱的代谢组分析中的滤噪作用评价

观察、比较正交信号校正(OSC)滤噪前后, 用不同的模式识别方法对正常成人血清代谢组¹H NMR谱进行分析的效果, 以探讨NMR代谢组学技术应用于临床研究和疾病早期诊断的可行性. 78例正常成人在采血前按常规要求禁食8 h, 记录血清一维600 MHz氢谱后, 分别采用主成分分析(PCA)、偏最小二乘法-判别分析(PLS-DA)以及簇类的独立软模式法(SIMCA)对氢谱进行模式识别分析. 结果表明: 虽然采血前并无其它诸如饮食、生活方式、生理周期等方面的严格限制, 采用OSC 滤噪后, PLS-DA能够完全区分不同性别的血清氢谱, 其判别能力优于PCA和SIMCA. 而且采用OSC滤噪与文献报道的未经OSC处理的PLS-DA法获得的与性别分类有关的主要NMR积分区段基本相同. 从OSC去除不同数目的隐变量后所致的PLS-DA模型的性能改变可见: OSC去除两个隐变量时, 前两个隐变量的特征值明显比后面的大; 剩余残差为20.82%, 即去除了79.18%的X变量中与反应变量Y不相关的系统变异. 此时PLS-DA计算所得的隐变量个数为1; 而不使用OSC或用OSC去除一个隐变量时, PLS-DA所得的隐变量个数分别为3和2. 作为PLS-DA模型质量的评价指标, R2X表示PLS-DA模型计算所获得的隐变量反映自变量X的变异的百分比, R2Y则表示隐变量反映因变量Y的变异的百分比, Q2 (cum)为交叉验证后PLS-DA模型所获隐变量能够预测X和Y变异的累计百分比. R2X在OSC去除两个隐变量时达到最低值, 表明此时PLS-DA计算模型包含的系统变异最少; R2Y与Q2 (cum)都达到80%以上并趋于稳定, 说明OSC去除两个隐变量时PLS-DA模型的质量优良. 显然, OSC可去除饮食、环境等因素的影响, 降低临床样本的不均一性, 这对于NMR代谢组学技术应用于临床研究至关重要. OSC滤噪去除的隐变量个数应根据剩余残差、去除隐变量的特征值大小、PLS-DA模型计算所得的隐变量个数和反映模型质量的相关指标加以判断.     

用聚合物先成物方法合成(Bi_(1.6)Pb_(0.4))Sr_2Ca_2Cu_(3.6)O_x超导材料

用聚合物—金属—络合物先成物(polymer—metal—complex precursor)方法,在小心控制煅烧条件下合成了(Bi_(1.6)Pb_(0.4))Sr_2Ca_2Cu_(3.6)O_x超导材料,产物有一个100K的零电阻转变温度[T_c(R=0)]。产物的X—光衍射峰相对强度表明,它只包含高—Tc相和低—Tc相,而且以高-Tc相为主。通过电阻测量、X—光衍射和元素分析,研究了产物的超导性能、结构和组成。     

结合电生孔技术的抗体-纳米TiO2靶向光敏杀癌细胞

报道了用免疫、电生孔和纳米TiO₂光催化组合技术进行杀伤结肠癌LoVo细胞的研究. 先把结合LoVo细胞表面CEA抗原的单克隆抗CEA抗体吸附在纳米TiO₂微粒表面, 抗体-纳米TiO₂复合微粒就会自动吸附到LoVo细胞的表面, 然后用电脉冲法使LoVo癌细胞的细胞膜上产生小孔, 促使纳米TiO₂微粒进入癌细胞内部. 最后在紫外光照射下使TiO₂纳米粒子在癌细胞内部发生光催化氧化作用, 杀伤癌细胞. 结果表明, 这种组合技术具有很高的杀癌细胞能力. 在仅含3.12 μg/mL抗体-纳米TiO₂的细胞培养液内和强度为4 mW/cm²的紫外光照射下, 可在30 min内将所有LoVo癌细胞杀死. 这种技术对LoVo癌细胞的杀伤力远高于对不表达CEA抗原的人正常TE353.sk细胞的杀伤力, 显示了组合技术杀癌细胞的高选择性. 因此, 这种组合技术有望成为治疗癌症的新方法, 值得进一步探索.     

Preparation and characterization of dealuminated metakaolin and its use in the transformation of waste plastics to aromatic hydrocarbons

Acid activated metakaolins (AAMKs) have been prepared by calcination of the natural clay at 600 degrees C to provide a metakolin which was then leached at 80 degrees C for 3 h using 1M, 2M, 3M, and 6M HCl. These materials were characterized and their ability to transform the off gases from HDPE decomposition into useful aromatic species was evaluated. The amount of adsorbed water and the number of acid sites increased with the severity of acid treatment. Variable temperature DRIFTS spectroscopy of pyridine treated samples revealed that both Br?nsted and Lewis acid centers were present until 425 degrees C. Pyridine bonded to the Lewis acid centers was more thermally stable. The AAMKs were all selective to the production of toluene with respectable, but lesser, amounts of xylenes and trimethylbenzenes. This selectivity contrasts with that of acid leached and pillared smectites which are selective toward trimethylbenzene.     

Stereoselective synthesis of cis-p-menth-8-ene-1,7-diol, cis-p-menthane-1,7-diol, and cis-p-menthane-1,7,8-triol

The natural products cis-p-menthane-1,7-diol (cis-IV), cis-p-menth-8-ene-1,7-diol (cis-I) and cis-p-menthane-1,7,8-triol (cis-II) are obtained starting from the corresponding cis-cyanohydrins, cis-2 and cis-7, respectively, by chemical transformation of the cyano into the hydroxymethyl group. The key step of the synthesis is the very high cis-selectivity (> or = 96 %) of the MeHNL-catalyzed HCN addition to 4-alkylcyclohexanones. From 4-isopropylcyclohexanone (1) the cyanohydrin cis-2 and from 4-(1-methylvinyl)cyclohexanone (6) the cyanohydrin cis-7 result almost quantitatively. Regioselective hydroxylation of cis-I affords the triol cis-II. X-ray crystal structure determinations of the final products confirm their cis-configuration.     

新型除草剂丙酯草醚A环14C均标记合成和鉴定

以U-¹⁴C-对氨基苯甲酸为前体, 通过酯化、缩合、还原和取代四步反应获得了A环¹⁴C均标记的丙酯草醚, 用PHPLC对其进行纯化. 采用HPLC-MS(ESI), MS(EI)和¹H NMR验证了其结构, 通过HPLC(外标法)确定其化学纯度大于98%; HPLC-LSC和TLC-IIA两种方法分析表明, 其放射化学纯度大于98%, 其比活度为1.089±0.011 mCi/mmol. 合成的化学收率和放化收率均为53%.     

A new simple and rapid electrochemical method for the determination of hydroxyl radical generated by Fenton reaction and its application

A simple and rapid electrochemical method to detect the hydroxyl radical is described. This method employed the reaction between.OH and dimethyl sulfoxide (DMSO) to generate quantitatively formaldehyde, which then reacted with hydrazine hydrochloride at pH 6.2. The product showed a second-order derivative cathodic wave with the peak potential of -1.08 V( vsSCE) by single sweep oscillopolarography. The electrochemical behavior of the product was investigated by single sweep oscillopolarography and cyclic voltammetry. The experimental conditions for the measurement were optimized and the scavenging activity of some flavonoids on hydroxyl radicals was studied.