UO2、UC2和UCO分子的结构和热力学性质

用密度泛函B3LYP方法,计算了UO2、UC2和UCO分子的结构和热力学函数,计算了固体U的振动内能Ev、振动和电子熵Sev,以及U在不同气氛（O2、C2、CO）中形成UO2、UC2和UCO晶体的ΔHfΘ、ΔSfΘ和ΔGfΘ.结果表明,UO2晶体最稳定.     

Synthesis, characterization and photodynamic activity of amino-substituted hypocrellin derivatives

Three new hypocrellin derivatives, amino- or amino acid-substituted on the side ring of hypocrellin B (HB), were synthesized by the reactions of HB with 3-methoxypropylamine, 6-aminohexanoic acid and gamma-amino-n-butyric acid, respectively. The structures of these compounds were characterized with proton nuclear magnetic resonance spectra, infrared spectra and mass spectra. The UV-visible absorption spectra, singlet oxygen-generating quantum yield and amphiphilicities of hypocrellin derivatives were measured and compared with HB, the parent compound. These derivatives showed strong absorption in the domain of the phototherapeutic window (600-900 nm) and improved amphiphilicity. HB and the derivatives were preliminarily tested for their photodynamic effects on human oral cavity epithelial carcinoma KB cell line in vitro. Two amino acid-substituted hypocrellins showed phototoxicity to the KB cell line. At an inhibitory dosage of 50% killing only 0.51 mumol L-1 compound 3 (or 0.88 mumol L-1 compound 2) and 0.5 J cm-2 irradiation were required. The hypocrellins exhibited some dark toxicity to the KB cell line. HB and amino acid-substituted hypocrellins showed lower dark toxicity to the KB cell line than amino-substituted hypocrellins in the assessment of cell survival.     

Determinations of combustion and formation enthalpies of C60 and C70

By using a micro-bomb calorimeter, the standard enthalpies of combustion of C₆₀ and C₇₀ have been determined to be - (25 947.1±8.5) and - (29 956.1 ± 8.9) kJ/mol respectively. A g. 1. c. analysis indicated that the amounts of residual organic solvents in the samples were very small, and their effects on the final results were negligible. The energy of combustion ofC60 determined in this work is in agreement in the uncertainty interval with that determined by means of traditional calorimeter using macro amount of sample. The enthalpies of formation of these two substances have been derived. The strain energies in the molecules of C₆₀ and C₇₀ were estimated by a bond energy scheme and by using corannulene as the model compound, the results estimated from different methods are very close. Project supported by the National Natural Science Foundation of China (Grant No. 29473143)     

Diterpene derivative and chromone from Hypericum perforatum

A novel diterpene derivative, 5-methyl-5-(4,8,12-trimethyl-tridecyl)-dihydro-furan-2-one (1) and a new chromone, 5-hydroxy-7-methoxy-3-methyl-chromen-4-one (2), along with a known compound, phytol (3) have been isolated from the aerial parts of Hypericum perforatum. Their structures were established on the basis of spectroscopic analysis and by comparison with published values.     

Synthesis and Characterization of a Novel Organic/Inorganic Hybrid Based on Octamolybdates and Benzimidazole Molecules [Hbenzimi]4 [(benzimi)2Mo8O26] · 2H2O (benzimi?=?benzimidazole)

A novel organic/inorganic compound [Hbenzimi]₄[(benzimi)₂Mo₈O₂₆] · 2H₂O (1) has been prepared hydrothermally and characterized by elemental analyses, i.r., x.p.s., t.g. and single crystal X-ray diffraction. The single crystal X-ray diffraction analysis reveals that compound (1) consists of the [Mo₈O₂₆]⁴⁻ cluster as the structural motif covalently linked by benzimidazole molecules and protonated benzimidazole molecules as charge compensation cations. It is interesting that the benzimidazole molecules were synthesized from 1,2-phenylenediamine and oxalic acid. The [Mo₈O₂₆]⁴⁻ polyoxoanions and organic ligands in compound (1) interact with each other via extensive hydrogen bonds to form a three-dimensional supramolecular framework.     

Optimized Separation of Nine Xanthones by Microemulsion Electrokinetic Chromatography

A microemulsion electrokinetic chromatography method has been firstly used for the separation of the therapeutically important xanthones from Securidaca inappendiculata. The separation of the nine xanthones was systematically optimized with respect to pH, composition of microemulsion,addition of cyclodextrins, applied voltage and column temperature. Baseline separation was successfully achieved for the nine xanthones, which was also compared with that by micellar electrokinetic chromtography.     

A radioanalytical technique to study the behavior of organic toxicants applied to a study of the photodegradation of 2,3,7,8-tetrachlorodibenzo-p-dioxin

A general method for tritium labeling of organic compounds by the use of thermal activation of tritium is described. It allows obtaining uniformly tritium-labeled organic compounds with high specific activity (up to 50 Ci/mmol) which permits tracing the majority of the biodegradation products of compounds studied. More than 40 compounds were labeled using this simple, rapid and inexpensive method. Separation of the biodegradation products is performed by thin layer chromatography. Quantification is performed by direct measurement of the radioactivity by liquid scintillation counting after transfer of the layer from TLC plates into scintillation vials, or by densitometry of autoradiographs. The technique is useful for a wide range of organic compounds, including ones with unknown structure, and can be applied to various in vivo and in vitro studies.     

A statistical method to detect chromosomal regions with DNA copy number alterations using SNP-array-based CGH data

Single nucleotide polymorphism (SNP) arrays were used to detect chromosomal regions with DNA copy number alterations. Current statistical methods for microarray-based comparative genomic hybridization (array-CGH) analysis generally assume certain relationships among adjacent markers on the same chromosome, and these assumptions may be questionable. For an SNP-array-based CGH study, multiple normal reference SNP arrays were collected. In order to utilize these normal reference SNP arrays, we derived an empirical distribution of signal ratios for each SNP marker. With an assumed threshold value for the overall error rate control and the defined signal ratio ranges for chromosomal amplification and deletion, we proposed a procedure to identify chromosomal alteration regions based on several bootstrapped one-sample t-tests and the false discovery rate control. When we have multiple arrays for different individuals with the same disease, our method can also be used to detect SNP markers for chromosomal alteration regions that are common among these individuals. We applied our method to a published SNP array data set for breast carcinoma cell lines. For an individual with breast cancer, numerous chromosomal alteration regions were identified. Compared to results of previous studies, our method identified more chromosomal alteration regions, with some being implicated in the literature to harbor genes associated with breast cancer. For multiple cancer arrays, our results suggested the existence of common chromosomal alteration regions. However, a high proportion of false positives also indicated that genetic variations among different individuals with breast cancer can be present.     

一些烷氯代烃标准蒸发焓的测定

在进行有机氯化物分子内非键合相互作用的热化学研究中, 为了排除分子间的相互作用, 需要准确的标准蒸发焓或升华焓, 以便把凝聚态的标准生成焓转变为气态的数据。文献中多氯代烷烃的蒸发焓数据不多, 其中由直接量热法得到的准确数据更少, 因此我们测量了一些多氯代烷烃的标准蒸发焓, 并对其规律作了一些探讨。     

Lithium dioxobis[trioxoiodato(V)]vanadate,Li[VO2(IO3)2]

The title compound represents a new structure type, in which distorted VO₆ octa­hedra are bridged by iodate groups to form infinite two‐dimensional [VO₂(IO₃)₂]⁻ layers that are separated by octa­hedrally coordinated Li⁺ cations.