Multiple catenanes derived from calix[4]arenes

A multicatenane is described in which two belts consisting of four annelated rings attached to the wide rims of two calix[4]arenes are interwoven in such a way that each ring of one belt penetrates two adjacent rings of the other belt and vice versa. The key step of the synthesis of this [8]catenane is the exclusive formation of preorganized heterodimers between a multimacrocyclic tetraurea calix[4]arene and an "open-chain" tetraurea calix[4]arene containing eight omega-alkenyl groups. When a tetraurea calix[4]arene containing four alkenyl groups is used, a bis-[3]catenane is formed analogously.     

X-ray diffraction and computation yield the structure of alkanethiols on gold(111)

The structure of self-assembled monolayers (SAMs) of long-chain alkyl sulfides on gold(111) has been resolved by density functional theory-based molecular dynamics simulations and grazing incidence x-ray diffraction for hexanethiol and methylthiol. The analysis of molecular dynamics trajectories and the relative energies of possible SAM structures suggest a competition between SAM ordering, driven by the lateral van der Waals interaction between alkyl chains, and disordering of interfacial Au atoms, driven by the sulfur-gold interaction. We found that the sulfur atoms of the molecules bind at two distinct surface sites, and that the first gold surface layer contains gold atom vacancies (which are partially redistributed over different sites) as well as gold adatoms that are laterally bound to two sulfur atoms.     

Molecular-Level Control over Surface Order in Self-Assembled Monolayer Films of Thiols on Gold

Long-chain omegahydroxyalkanethiols [HS(CH(2))nOH] coordinate to gold surfaces through the sulfur atom and produce ordered, hydrophilic monolayers in which the hydroxyl groups are exposed at the outer surface. Coadsorption of two omega-hydroxyalkanethiols of different chain lengths n resulted in the formation of a monolayer having a disordered surface region that was markedly less hydrophilic than the homogeneous, hydroxylic surface formed from either pure compound. By controlling the composition of the monolayer, it was also possible to control simultaneously the degree of order in the surface and its hydrophilicity. In the monolayers containing a mixture of alkanethiol components, these components apparently did not phase-segregate into macroscopic islands, but were dispersed on a molecular scale. assistance and many useful discussions.     

Synthesis of inorganic fullerene-like molecules

The reaction of [Cp*Fe(eta5-P5)] with Cu(I)Cl in solvent mixtures of CH2Cl2/CH3CN leads to the formation of entirely inorganic fullerene-like molecules of the formula [[Cp*Fe(eta5:eta1:eta1:eta1:eta1:eta1-P5)]12[CuCl]10[Cu2Cl3]5[Cu(CH3CN)2]5] (1) possessing 90 inorganic core atoms. This compound represents a structural motif similar to that of C60: cyclo-P5 rings of [Cp*Fe(eta5-P5)] molecules are surrounded by six-membered P4Cu2 rings that result from the coordination of each of the phosphorus lone pairs to CuCl metal centers, which are further coordinated by P atoms of other cyclo-P5 rings. Thus, five- and six-membered rings alternate in a manner comparable to that observed in the fullerene molecules. The so-formed half shells are joined by [Cu2Cl3]- as well as by [Cu(CH3CN)2]+ units. The spherical body has an inside diameter of 1.25 nanometers and an outside diameter of 2.13 nanometers, which is about three times as large as that of C60.     

Free energy and temperature dependence of electron transfer at the metal-electrolyte interface

The rate constant of the electron-transfer reaction between a gold electrode and an electroactive ferrocene group has been measured at a structurally well-defined metal-electrolyte interface at temperatures from 1 degrees to 47 degrees C and reaction free energies from -1.0 to +0.8 electron volts (eV). The ferrocene group was positioned a fixed distance from the gold surface by the self-assembly of a mixed thiol monolayer of (eta(5)C(5)H(5))Fe(eta(5)C(5)H(4))CO(2)(CH(2))(16)SH and CH(3)(CH(2))(15)SH. Rate constants from 1 per second (s(-1)) to 2 x 10(4) s(-1) in 1 molar HClO(4) are reasonably fit with a reorganization energy of 0.85 eV and a prefactor for electron tunneling of 7 x 10(4) s(-1) eV(-1). Such self-assembled monolayers can be used to systematically probe the dependence of electron-transfer rates on distance, medium, and spacer structure, and to provide an empirical basis for the construction of interfacial devices such as sensors and transducers that utilize macroscopically directional electron-transfer reactions.     

响应面优化超声波辅助[Bmim]Cl-K2HPO4双水相提取黄秋葵多糖

  目的  探讨超声波辅助[Bmim]Cl-K₂HPO₄提取黄秋葵多糖的最佳工艺。  方法  采用浊点滴定法，比较[Bmim]Cl-(NH₄)₂SO₄、[Bmim]Cl-Na₂HPO₄、[Bmim]Cl-Na₂CO₃和[Bmim]Cl-K₂HPO₄等4种双水相体系的分相能力与萃取能力，确定[Bmim]Cl-K₂HPO₄为最佳双水相体系。以黄秋葵Abelmoschus esculentus为原料，采用超声波辅助[Bmim]Cl- K₂HPO₄提取黄秋葵多糖，探讨K₂HPO₄质量分数、提取时间、提取温度、液固比、[Bmim]Cl质量分数等5个单因素对提取率的影响。在各单因素试验最佳条件的基础上，进行响应面Box-Behnken设计，优化黄秋葵多糖提取工艺。  结果  各因素对提取率影响大小依次为液固比、[Bmim]Cl质量分数、提取温度、提取时间、K₂HPO₄质量分数；最佳工艺条件为5 mL质量分数71.94%的离子液体[Bmim]Cl，5 mL质量分数22.31%的K₂HPO₄双水相体系中，提取时间29.36 min，提取温度55.69 ℃，液固比25.00 mL·g?1，黄秋葵多糖提取率为29.12%。验证平均值为31.22%，相对标准偏差为3.70%。  结论  超声波辅助[Bmim]Cl-K₂HPO₄提取工艺具有提取率高、时间短、离子液体可回收等优点，可用于工业化生产。图8表3参24     

荧光光谱滴定法测定痕量的双甲脒

通过荧光光谱滴定法研究了脱叔丁基杯[4]芳烃与双甲脒之间的相互作用。实验表明在加入不同量的双甲脒后脱叔丁基[4]芳烃的荧光发生猝灭,由此建立了一种快速简便的测定双甲脒的方法,该方法的线性范围是1.00～60.0μg/mL,添加回收试验表明该方法可行。     

"Coulomb Staircase" at Room Temperature in a Self-Assembled Molecular Nanostructure

Double-ended aryl dithiols [alpha,alpha'-xylyldithiol (XYL) and 4,4'-biphenyldithiol] formed self-assembled monolayers (SAMs) on gold(111) substrates and were used to tether nanometer-sized gold clusters deposited from a cluster beam. An ultrahigh-vacuum scanning tunneling microscope was used to image these nanostructures and to measure their current-voltage characteristics as a function of the separation between the probe tip and the metal cluster. At room temperature, when the tip was positioned over a cluster bonded to the XYL SAM, the current-voltage data showed "Coulomb staircase" behavior. These data are in good agreement with semiclassical predictions for correlated single-electron tunneling and permit estimation of the electrical resistance of a single XYL molecule (approximately18 ± 12 megohms).     

Scanning tunneling microscopy of galena (100) surface oxidation and sorption of aqueous gold

Scanning tunneling microscopy was used to characterize the growth of oxidized areas on galena (100) surfaces and the formation of gold islands by the reductive adsorption of AuCl(4)(-) from aqueous solution. The gold islands and galena substrate were distinguished by atomic resolution imaging and tunneling spectroscopy. Oxidized areas on galena have [110]-trending boundaries; gold islands elongate along [110] directions. However, there are no obvious structural registry considerations that would lead to elongation of gold islands in a [110] direction. Instead, it is probable that a direct coupling of gold reduction and sulfide surface oxidation controls the initial formation of gold islands. Gold islands grow less quickly on preoxidized galena surfaces and show no preferred direction of growth.     

响应面分析法优化磁螺菌(M.gryphiswaldense MSR-1)的培养条件

[目的]为了得到磁螺菌Magnetospirillum.gryphiswaldense MSR-1的最佳培养条件。[方法]通过单因素试验分析,确定最适于磁螺菌M.gryphiswaldense MSR-1生长的碳源和氮源分别是乳酸钠和氯化铵,综合考虑pH、乳酸钠和氯化铵3个因素对MSR-1生长的影响,用Design-Expert.8.05b软件的Box-Behnken进行响应面分析,优化MSR-1的培养条件,得到了菌体生长模型,同时取得模型最优值时各因素的水平。[结果]当乳酸钠浓度为3.17 g/L,氯化铵浓度为0.43 g/L,pH为6.98时,理论预测的OD600值为0.797,并在该条件下进行了3次重复验证试验,OD600的平均值为0.792,与理论值基本吻合。[结论]在菌体生长过程中,氯化铵和pH及乳酸钠和pH对菌体的交互作用显著,乳酸钠和氯化铵对菌体生长的交互作用不显著。菌体生长模型达到显著水平,可以对磁螺菌M.gryphiswaldense MSR-1在不同条件下的生长情况进行分析与预测。     

EuTiNiO4Cl纳米晶的抗凝血作用研究

[目的]研究EuTiNiO4Cl纳米晶的抗凝血作用。[方法]利用溶胶凝胶法制备EuTiNiO4Cl纳米晶,在一定温度下真空干燥凝胶,在不同温度下进行X射线衍射分析,之后用不同浓度的EuTiNiO4Cl纳米晶对体重为(20±2)g的健康小白鼠进行灌胃,以血液出现拉丝现象作为测定血液凝固的指标,研究EuTiNiO4Cl纳米晶的抗凝血作用。[结果]在350、400和450℃时纳米晶的XRD峰非常宽,说明此温度下其晶型为不定型;在500、600和700℃时纳米晶的XRD峰高而尖;EuTiNiO4Cl纳米晶的粒径随温度的升高而增大,其晶型由不定型变为多晶型。抗凝血试验表明EuTiNiO4Cl纳米晶具有良好的抗凝血作用。当EuTiNiO4Cl纳米晶浓度为2.5×10-3mol/L时,其抗凝血效果最好。[结论]EuTiNiO4Cl纳米晶的抗凝血性能良好。     

Imaging surface atomic structure by means of auger electrons

Measurements of the complete angular distribution of Auger electrons emitted from well-defined platinum[111] single-crystal surfaces have led to the discovery that the distributions are composed of "silhouettes" of surface atoms "back lit" by emission from atoms deeper in the solid. Theoretical simulations of Auger electron angular distributions based upon atomic point emitters and spherical atomic scatterers of uniform cross section are in close agreement with these experimental results, but opposite to previous theoretical predictions. In view of the definitive results obtained and the straightforward agreement between theory and experiment, angular distribution Auger microscopy (ADAM) is useful for direct imaging of interfacial structure and investigation of electron-solid interactions in the physical and biological sciences and engineering. Applicability of ADAM is illustrated by images obtained for monolayers of silver and iodine on platinum[111].     

Storage of methane and freon by interstitial van der Waals confinement

A known host-guest assembly, organized only by means of relatively weak dispersive forces, exhibits hitherto unappreciated thermal stability. The hexagonal close-packed arrangement of calix[4]arene contains lattice voids that can occlude small, highly volatile molecules. This host-guest system can be exploited to retain a range of freons, as well as methane, not only well above their normal boiling points, but also at relatively high temperatures and low pressures. The usually overlooked van der Waals interactions in organic crystals can indeed be used in a highly stable supramolecular system for gas storage.     

“黄金冠”桃及其品系亲缘关系分析研究

[目的]分析黄金冠桃及其品系的亲缘关系。[方法]应用聚丙烯酰胺凝胶电泳(PAGE)技术,对锦绣、黄金冠、黄桃19、锦黄2号、锦黄3号和锦黄4号(均属于黄桃)6个品种(品系)进行过氧化物酶同工酶电泳分析,并通过聚类分析法对其亲缘关系进行研究。[结论]结果表明,黄金冠与锦绣亲缘关系最为相近,与其他品系间的亲缘关系较远。[结论]该研究对黄金冠及其品系的分类、品种鉴定、新品种选育及其优势利用提供科学依据。     

乌兰布和沙漠地区灌水对成龄霸王生长及光合作用的影响

[目的]揭示灌水对成龄霸王生长及光合作用的影响。[方法]采用野外试验,通过对中国林科院沙林中心第一实验场植物园中成龄霸王[Zygophyllum xanthoxylum(Burge)Maxim]进行不同灌水量处理,研究人工深层坑渗灌条件下灌水量[开春水:W_115 kg/株、W_245 kg/株、W_375 kg/株、W_4150 kg/株,埋冬水:W_575 kg/株,无灌溉(CK)]对成龄霸王地上生物量、叶片相对含水量(RWC)、叶片净光合速率(Pn)、蒸腾速率(Tr)和水分利用效率(WUE)的影响。[结果]随着灌水量的增加,成龄霸王地上生物量不断增加;各处理的叶片RWC从大到小依次为W_3、W_2、W_4、CK、W_5、W_1;自然条件和人工灌水条件下,霸王叶片Pn、Tr的日变化均呈"双峰"曲线,且有明显的"午休"现象。各处理Pn日均值从大到小依次为W_3、W_2、W_4、W_1、CK、W_5;Tr日平均值从大到小依次为W_3、W_2、W_1、W_4、W_5、CK。WUE日平均值从大到小依次为W_3、W_2、CK、W_1、W_5、W_4。[结论]综合分析,最适宜的灌水时间是成龄霸王萌芽期,最佳的坑渗灌量为开春水75 kg/株。     

猪CD127流式单克隆抗体的研制

[目的]研制出猪CD127(调节因子IL-7受体α链)流式单克隆抗体,为研究分析猪淋巴细胞亚群,尤其是猪Treg细胞亚群提供流式细胞分析抗体,也为进一步探究猪抗病性状与免疫机制间的关系打下基础.[方法]克隆猪CD127基因片段,通过原核载体诱导表达出相应的融合蛋白,以纯化后的融合蛋白免疫Balb/c小鼠,然后取其脾细胞与SP2/0骨髓瘤细胞融合,综合ELISA和流式细胞仪检测筛选出亚克隆抗体,并采用Western blotting验证所得亚克隆抗体能否与猪淋巴细胞上的CD127特异性结合.[结果]猪CD127基因cDNA全长1999 bp,第49~1428 bp为开放阅读框(ORF),编码459个氨基酸,其中前21位氨基酸为信号肽,成熟肽N端第1~219位氨基酸为胞外蛋白,第220~242位氨基酸为跨膜蛋白,第243~459位氨基酸为胞内蛋白.以pET28a和pET32a原核载体诱导表达CD127胞外片段可获得大小介于34~43 kD的融合蛋白,经Ni亲和层析柱纯化后用于免疫Balb/c小鼠,6只免疫小鼠血清中的多克隆抗体均能对猪淋巴细胞中的CD3阳性细胞(CD3+)进行共标记,其中以M2和M4两只免疫小鼠抗血清对CD3+的共标记效果较优,分群清晰;但流式细胞仪检测发现,仅2.3%的CD3+能与M2混合池培养基上清液中的分泌抗体共标记,而67.0%的CD3+能与M4混合池培养基上清液中的分泌抗体共标记,且分群清晰.从M4混合池中筛选出6株效价稳定的亚克隆细胞株(1E2、1D8、2F3、2F8、3C6和4E1),且以1D8、2F3、2F8和3C6亚克隆抗体标记的CD3+较多,其培养基上清液中的分泌抗体在猪胸腺和肌肉样品中均能检测出大小约50 kD的单一目的条带.[结论]制备获得的猪CD127流式单克隆抗体可与T淋巴细胞表面的IL-7受体特异性结合,同时在流式细胞仪检测过程中可用于猪Treg细胞亚群检测.     

Evidence for coherent proton tunneling in a hydrogen bond network

We observed coherent proton tunneling in the cyclic network of four hydrogen bonds in calix[4]arene. The tunneling frequency of 35 megahertz was revealed by a peak in the magnetic field dependence of the proton spin-lattice relaxation rate measured with field-cycling nuclear magnetic resonance in the solid state at temperatures below 80 kelvin. The amplitude of the coherent tunneling peak grows with temperature according to a Boltzmann law with energy D/kB = (125 +/- 10) kelvin (where kB is Boltzmann's constant). The tunneling peak can be interpreted in the context of level crossings in the region where the tunneling frequency matches the proton Larmor frequency. The tunneling spectrum reveals fine structure that we attribute to coupling between the hydrogen bonds in the network. The characteristics of the tunneling peak are interpreted in the context of the potential energy surface experienced by the hydrogen atoms in the network.     

A stable silicon(0) compound with a Si=Si double bond

Dative, or nonoxidative, ligand coordination is common in transition metal complexes; however, this bonding motif is rare in compounds of main group elements in the formal oxidation state of zero. Here, we report that the potassium graphite reduction of the neutral hypervalent silicon-carbene complex L:SiCl4 {where L: is:C[N(2,6-Pri2-C6H3)CH]2 and Pri is isopropyl} produces L:(Cl)Si-Si(Cl):L, a carbene-stabilized bis-silylene, and L:Si=Si:L, a carbene-stabilized diatomic silicon molecule with the Si atoms in the formal oxidation state of zero. The Si-Si bond distance of 2.2294 +/- 0.0011 (standard deviation) angstroms in L:Si=Si:L is consistent with a Si=Si double bond. Complementary computational studies confirm the nature of the bonding in L:(Cl)Si-Si(Cl):L and L:Si=Si:L.     

离子液体[C_(16)mim]Cl对泥鳅胚胎与仔鱼的毒性

为了研究离子液体[C_(16)mim]Cl的生物毒性作用,以泥鳅(Misgurnus anguillicaudatus Cantor)胚胎和仔鱼为受试动物,分别以胚胎发育的囊胚期、原肠胚期、神经胚期和尾芽期4个发育时期以及孵出期和孵出3 d的仔鱼作为处理的起始点进行急性毒性试验。结果显示,随着[C_(16)mim]Cl浓度的增加和处理时间的延长,泥鳅胚胎的孵化率逐渐下降,畸形率则在逐步升高;其中,刚孵出的仔鱼24 h与48 h的半数致死浓度(LC_(50))及安全浓度(SC)分别为0.555、0.453、0.091 mg/L;孵出3 d的仔鱼24 h与48 h的LC_(50)及SC分别为0.444、0.273、0.031 mg/L。表明在较低剂量内,离子液体[C_(16)mim]Cl对泥鳅胚胎及其仔鱼的发育表现出明显的致畸与致死作用,并且该毒性作用具有显著的剂量-效应关系。     

芝麻与花生间作套种增效技术研究(英文)

[目的]建立较优的芝麻与花生间作套种的配比及施肥技术。[方法]采用双因素(2种施肥方法和5种配比)随机区组设计,10个处理,3次重复,共30个小区,小区面积12.0m2。2种施肥方法分别为C1[底肥(540g/小区,复合肥+追肥(90g/小区,尿素)]和C2[全部作底肥(540g小区,复合肥)]。五种配比(芝麻:花生)分别为M1(2∶4),M(22∶6),M(31∶4),单作芝麻(CK1),单作花生(CK2)。[结果]6行花生2行芝麻,每小区施底肥540g,复合肥+追肥90g尿素处理,产值和土地当量比(LER)最高,分别为22378.68元/hm2和1.56;芝麻产量641.64kg/hm2、花生产量2506.67kg/hm2;产投比4.94;较单作花生、芝麻收益增加32.32%、95.97%。[结论]该研究可以为找到芝麻与花生的最佳种植配比和合理施肥提供理论依据。