Cucurbit[6]uril pseudorotaxanes: distinctive gas-phase dissociation and reactivity

Cucurbit[6]uril forms a doubly charged complex with 1,4-butanediammonium cation that is observed using electrospray ionization Fourier transform mass spectrometry. Such 1:1 complexes are not observed for the smaller cucurbit[5]uril, which forms a 2:1 ammonium:cucurbituril complex instead. The 1:1 complex with cucurbit[6]uril is difficult to fragment via collisional activation; when it does fragment, both breakup of the cucurbituril cage and loss of the amine are observed. Further, the complex reacts with tert-butylamine via slow adduction. In contrast, nonrotaxane analogues (such as doubly charged 2:1 complexes of either protonated 1,4-butanediamine or protonated ethylenediamine with cucurbit[6]uril) fragment via easy loss of the intact amine upon collisional activation and react with tert-butylamine via rapid displacement of the original amine. On the basis of stoichiometry, fragmentation behavior, and reactivity, we conclude that the doubly charged complex of cucurbit[6]uril with 1,4-butanediammonium is a gas-phase pseudorotaxane.     

Total synthesis of (-)-laulimalide

(-)-Laulimalide (1), a structurally novel macrolide isolated in trace amounts from marine sponges, promotes abnormal tubulin polymerization and apoptosis in vitro, with a similar mode of action to that of Taxol(R), but with potentially less susceptibility to multidrug resistance. Herein, a flexible and convergent asymmetric synthesis of (-)-laulimalide is described. This synthesis featured a highly diastereoselective Sakurai reaction of 2 with 3 and a regioselective macrolactonization of an unprotected vicinal diol. Laulimalide was synthesized in 25 steps (longest linear; 36 overall) in 3.5% overall yield, providing a uniquely short and efficient route to 1 and its analogues.     

Recombinant squalene synthase. Synthesis of non-head-to-tail isoprenoids in the absence of NADPH

Squalene synthase (SQase) catalyzes two consecutive reactions in sterol biosynthesis. The first is the condensation of two molecules of farnesyl diphosphate (FPP) to form a cyclopropylcarbinyl intermediate, presqualene diphosphate (PSPP). The subsequent conversion of PSPP to squalene (SQ) involves an extensive rearrangement of the carbon skeleton and a NADPH-dependent reduction. Incubation of a truncated soluble form of recombinant yeast SQase with FPP in buffer lacking NADPH gave (1R,2R,3R)-PSPP. As the incubation continued, SQase catalyzed the subsequent conversion of PSPP to a mixture of triterpenes. Two of the major products, (Z)-dehydrosqualene (DSQ) and (R)-12-hydroxysqualene (HSQ), have the same 1'-1 linkage between the farnesyl units from FPP that is found in squalene. The other major product, (10S,13S)-10-hydroxybotryococcene (HBO), has a 1'-3 linkage between the farnesyl units. Small quantities of (S)-HSQ and (10R,13S)-HBO were also formed. Three additional triterpenes, the allylic isomers of HSQ and HBO, and an unidentified alcohol were produced in minor amounts. A methyl ether corresponding to HSQ was detected when methanol was present in the incubation buffer. These compounds are the expected "solvolysis" products from PSPP. They provide strong support for mechanisms that propose cyclopropylcarbinyl cations as intermediates in the SQase-catalyzed rearrangement of PSPP to SQ and unambiguously demonstrate that the catalytic machinery of SQase is capable of synthesizing a variety of irregular isoprenoids.     

硼化合物的研究——Ⅴ.氢硼酸π-芳烃-π-环戊二烯基铁的合成和性质

本文研究了氢硼酸根(B_(12)H_(12)~(2-)、B_(10)H_(10)~(1-)、B_(11)H_(14)~-)和π-芳烃-π-环戊二烯基铁阳离子的反应,合成了36个氢硼酸π-芳烃-π-环戊二烯基铁化合物。通过元素分析和红外光谱测定确定了化合物的组成。部份化合物还作了~1H NMR鉴定。对化合物的性质,包括它们的热行为,进行了较详细的研究。DTA仪测得的结果表明,(1)当阳离子相同时,化合物的热稳定性的顺序为:[ArFeC_5H_5]_2B_(12)H_(12)>[ArFeC_5H_5]_2B_(10)H_(10)>[ArFeC_5H_5]B_(11)H_(14);(2)当氢硼酸根相同时,其热稳定性受芳环上取代基的影响。     

乳状液法制备憎液溶胶Ⅰ.BaCO_3均匀粒子的制备

均匀胶体粒子的形成，除与反应条件（反应物浓度、陈化时间和温度、介质种类等）有关外，反应体系的环境也影响最终产物的形态，《至结晶结构．气溶胶法和微乳液法正是利用微环境中的‘水池效应”；分别制备出球形亚微米和纳米级的均匀粒子［‘－‘］、这些方法与水解法和相转化法等方法比较，反应物浓度要大几个数量级，而反应时间却短很多，因而受到研究人员的关注．乳状液也能提供亚微米、微米及以上级的微环境，因此，可以应用O／W乳状液乳液中的聚合反应制备亲液的分散体系．然而，极少有关利用w／O乳状液制备僧液溶胶的报导问；最近…     

二茂钛苄氧基衍生物的合成及性质研究

Ｃｐ２ＴｉＣｌ２及（ＭｅＣｐ）２ＴｉＣｌ２在Ｅｔ３Ｎ或ＮａＮＨ２存在下与苄醇类化合物反应，高产率地合成了６个未见文献报道的二茂钛（Ⅳ）苄氧基衍生物，甲基二茂钛（Ⅳ）苄氧基化合物，经元素分析，ＨＮＭＲ和ＩＲ光谱确定了化合物的结构，并对其部分性质进行了讨论。     

Synthesis and structure of The Novel Layered Phase CsTi2Cl7

Reactions in the CsCl? TiCl₃? Ti system afford CsTiCl₃ (CsNiCl₃ type, a = 7.3086(7) Å, c = 6.0670(8) Å) and the new phase CsTi₂Cl₇, the structure of which was determined by single crystal X-ray diffraction means (P2/c, Z = 2, a = 7.0076(4) Å, b = 6.2256(4) Å, c = 12.000(2) Å, β = 92.175(6)°, R/R_w = 0.026/0.035 for 1403 reflections, 2Θ ≤ 60°, MoKα). The structure can be generated by condensation of TiCl₆ groups first through cis edges to form TiCl₂Cl_4/2 ribbons and then by interconnection of these with one chlorine per titanium to give layers, viz., [Ti(Cl)Cl_4/2Cl_1/2]^?. The remaining, singly bonded chlorine projects into the interlayer region and has a Ti? Cl distance 0.208 Å less than the average for the five, 2.466 Å, reflecting significant pi bonding of the chlorine to titanium. Possible interaction of the d orbitals on adjacent titanium(III) atoms is also considered.     

O(3P)原子与3-戊酮反应速率常数与温度关系的测定

由于燃烧机理和大气化学过程研究的需要,人们对有机化合物分子,如烷烃、烯烃及其衍生物与一些自由基,如O、OH和卤素原子的反应速率常数进行了广泛的测定。但酮类分子与这些自由基的研究则报道得很少,尽管人们早已发现酮类化合物是碳氢化合物被NO_x光氧化过程中产生的中间化合物。就我们所知,除有少量的关于O(~3P))原子与酮类分子反应速率常数测定的文献报道外,我们在前文中报道了用流动微波放电——化学发光方法测     

微量热法研究γ-Mo2N催化剂表面氢的微分吸附热

Differential heats of H 2 adsorption on γ-Mo2N catalysts were studied by using microcalorimetry. Samples with high and medium surface areas (90 and 17 m2•g -1 ) present a homogeneous energetic distribution of surface sites, which corresponds with the preferential orientation of their (200) planes. Molybdenum nitride with low surface area (8 m2•g -1 ) displays a heterogeneous energetic distribution of H 2 adsorption sites. The higher initial differential heat of hydrogen adsorption observed for the low surface Mo nitride was attributed to species adsorbed on surface sites associated with the (111) plane.     

ESR studies of γ-irradiated histone octamer and the histone H3

ESR spectrum of neat histone H3 γ-irradiated and observed at 77 K with low microwave power and modulation amplitude showed multiple resolved structure depicting nonequivalent interaction of the unpaired electron located at amido-carbonyl radical anion [– )NH–] of the peptide backbone with adjacent –NH– group and the β-proton of –CH group. The predominance of amido-carbonyl radical anion is in good accord with the expected partition of secondary electrons amongst the various electrophilic groups including peptide carbonyl and aromatic acid residues. Following a gradual rise of annealing temperature to room temperature, a double splitting spectrum from the well known -carbon amido radical was evolved.