α-羟基膦酸酯芳甲酸酯的合成、晶体结构和质谱裂解规律研究

α-羟基膦酸酯与各种取代苯甲酸或吡啶甲酸,通过酰氯或缩合剂的作用,合成了一系列的O,O-二烷基-α-苯基-α-(取代芳基甲酸酯基)-甲基膦酸酯的衍生物.它们的合成收率为61%～84%,这些化合物的结构经过核磁(1HNMR,13CNMR和31PNMR)、红外、质谱、元素分析或高分辨质谱确证,同时化合物C1的结构在晶体结构解析上进一步得到证实.利用多级质谱分析了化合物C2,C5和C8的质谱裂解规律,解释了重排离子的形成机制.     

A cyclopenta-fused dibenzo[b,d]thiophene-co-phenanthrene macrocyclic tetraradicaloid

A cyclopenta-fused macrocyclic tetraradicaloid, MC4-S, containing alternating phenanthrene (Phen) and dibenzo[b,d]thiophene (DBTh) units was synthesized and isolated in single-crystal form. Compared with its all-carbon isoelectronic structure, CPTP-M, the incorporation of two sulfur atoms leads to a smaller radical character and a larger singlet–triplet energy gap. X-ray crystallographic analysis reveals that the spin–spin coupling through the DBTh unit is stronger than that through the Phen moiety. In addition, the electron-rich sulfur atoms also raise the energies of both the HOMO and LUMO in MC4-S, but the overall optical and electronic energy gaps are close to that of the CPTP-M. MC4-S displays global anti-aromaticity according to the NMR measurements and theoretical calculations (NICS, ACID and 2D ICSS), with a 36π ring current circuit along the all-carbon periphery excluding the two sulphur atoms. Its dication becomes globally aromatic due to the existence of a dominant 34π-conjugation pathway. This study sheds some light on the effect of heteroatoms on the electronic properties of open-shell polyradicaloids.

The first member of sulfur-heterocycloarene neutral tetraradicaloids, MC4-S, was synthesized in crystalline form, which displays strong global anti-aromaticity and unique properties.     

Selective C-C bonds formation,N-alkylation and benzo[d]imidazoles synthesis by a recyclable zinc composite

Earth abundant metals are much less expensive, promising, valuable metals and could be served as catalysts for the borrowing hydrogen reaction, dehydrogenation and heterocycles synthesis, instead of noble metals. The uniformly dispersed zinc composites were designed, synthesized and carefully characterized by means of XPS, EDS, TEM and XRD. The resulting zinc composite showed good catalytic activity for the N-alkylation of amines with amines, ketones with alcohols in water under base-free conditions, while unsaturated carbonyl compounds could also be synthesized by tuning the reaction conditions. Importantly, it was the first time to realize the synthesis of 2-aryl-1H-benzo[d]imidazole derivatives by using this zinc composite under green conditions. Meanwhile, this zinc catalyst could be easily recovered and reused for at least five times.     

对微量元素与恶性肿瘤关系的新认识

微量元素与恶性肿瘤关系是当前十分引人注目的研究课题．MEDLINE数据库显示．近5年中硒、锌、铜与肿瘤关系的文章最多．微量元素与恶性肿瘤相关性有三种可能,即微量元素的丰缺是恶性肿瘤的结果.是肿瘤发生的条件因素或病因．微量元素之间的关系相当复杂．既拮抗。又协同，微量元素的研究刚起步．取样和检测方法等均需标准化．其与恶性肿瘤的发生和发展的机理更需积极研究.     

金纳米棒/石墨相氮化碳复合薄膜的制备及其光电化学性能

石墨相氮化碳(g-C₃N₄)作为一种新型的非金属有机半导体材料在光催化领域受到了人们的广泛关注。 为进一步改善它的光电化学性能,本文利用种子生长法和一锅法相结合制备了Au纳米棒/g-C₃N₄复合材料。 结果表明,金纳米棒降低了载流子的复合率,使复合材料表现出了较好的光电化学性能。 该材料光电流密度可达到17.18 μA/cm²(相对于可逆氢电极),是纯的石墨相氮化碳材料的2.5倍。     

细胞代谢组学用于羽扇豆醇干预人乳腺癌细胞MCF-7的机理探究

应用基于气相色谱-质谱联用（GC-MS）的代谢组学方法结合细胞周期实验,研究羽扇豆醇体外抑制人乳腺癌细胞MCF-7增殖的作用机理。代谢组学的研究结果表明：通过正交偏最小方差判别分析（OPLS-DA）可以很好地区分羽扇豆醇作用的MCF-7细胞代谢谱与对照组细胞代谢谱,模型参数为：R²Ycum=0.988,Q²Ycum=0.964。VIP（variable importance in the projection）值大于1的差异代谢物进一步用t检验进行单位分析,选择t<0.05（VIP>1）的代谢物作为羽扇豆醇作用组的生物标志物,得到琥珀酸、磷酸、亮氨酸、异亮氨酸等11种代谢差异物。结合羽扇豆醇将细胞周期抑制在G1期这一现象,推测羽扇豆醇可能是主要抑制了三羧酸循环中的琥珀酰辅酶A的生成和底物磷酸化生成ATP的反应来抑制MCF-7细胞的增殖。本实验从代谢组学角度为乳腺癌抗肿瘤机制提供新的线索。     

Synthesis and optical properties of white phosphorescent carbazole - iridium copolymers

A series of novel carbazole-iridium copolymers have been designed and synthesized by the combination of blue-emitting acrylate carbazole M1 with hole transporting property and yellow-emitting cyclometalated iridium complex M2 containing 2-phenylpyridine as main ligand and acrylic acid as auxiliary ligand. The results showed that the blue carbazole host resulted in an efficient energy transfer to the yellow iridium complex guest, and when the feed molar ratio of M1 to M2 was 99:1, the emission spectrum of the copolymer presented a broad peak emission which can cover the whole visible range from 400 to 700 nm to obtain a nearly white copolymer material with the CIE coordinates of (0.30, 0.31), as a consequence of polymerized units luminescence, host-guest energy transfer and conjugation degree. Nevertheless, the host-guest energy transfer resulted in green emission about 524 nm of copolymer as the proportion of iridium complex monomer increased. The fluorescence quantum yields of the copolymers were significantly improved compared to the iridium complex monomer.     

CaxSr1—xS：Bi,Tm,Cu和CaS：Eu荧光材料的研究

所作的一部分工作是对长余辉的荧光材料ＣａｘＳｒ１－ｘＳＢｉ，Ｔｍ，Ｃｕ（ｘ＝０，０．７５，１）进行了研究．ＣａＳ和ＳｒＳ两种基质材料高温互溶后，因为基质的晶体微结构上的变化引起Ｂｉ３＋离子荧光效应的变化，即发光的发射波数发生改变．另一部分工作是对ＣａＳＥｕ加入陷阱机制后发光效应的研究．新的陷阱机制的引进，使得其余辉效应有较大的延长．     

Layered Double Hydroxide Nanosheets with Multiple Vacancies Obtained by Dry Exfoliation as Highly Efficient Oxygen Evolution Electrocatalysts

Layered double hydroxides (LDHs) with two-dimensional lamellar structures show excellent electrocatalytic properties. However, the catalytic activity of LDHs needs to be further improved as the large lateral size and thickness of the bulk material limit the number of exposed active sites. However, the development of efficient strategies to exfoliate bulk LDHs into stable monolayer LDH nanosheets with more exposed active sites is very challenging. On the other hand, the intrinsic activity of monolayer LDH nanosheets can be tuned by surface engineering. Herein, we have exfoliated bulk CoFe LDHs into ultrathin LDH nanosheets through Ar plasma etching, which also resulted in the formation of multiple vacancies (including O, Co, and Fe vacancies) in the ultrathin 2D nanosheets. Owing to their ultrathin 2D structure, the LDH nanosheets expose a greater number of active sites, and the multiple vacancies significantly improve the intrinsic activity in the oxygen evolution reaction (OER).