Iron-stabilized carbocations as intermediates for organic synthesis

Attachment of a transition metal moiety to an olefinic ligand presents the organic chemist with unequaled opportunities to control the regio- and stereospecificities of bond formation. Applications of cationic dienyliron-carbonyl complexes to a range of natural product syntheses have been developed. These applications show how the iron-carbonyl unit directs the regio- and stereochemistry of nucleophile addition. They also show that the iron-carbonyl unit can be used to stabilize otherwise inaccessible carbocations, thereby making them readily available as synthetic intermediates.     

Synthesis beyond the molecule

Weak, noncovalent interactions between molecules control many biological functions. In chemistry, noncovalent interactions are now exploited for the synthesis in solution of large supramolecular aggregates. The aim of these syntheses is not only the creation of a particular structure, but also the introduction of specific chemical functions in these supramolecules.     

Molecular weight determinations of proteins by californium plasma desorption mass spectrometry

The plasma desorption mass spectrometry method is used to determine the molecular weights of larger molecules than before, to determine the molecular weights of proteins and peptides in mixtures, and to monitor protein modification reactions. Proteins up to molecular weight 25,000 can now be studied with a mass spectrometric technique. Protein-peptide mixtures that could not be resolved with conventional techniques were successfully analyzed by this technique. The precision of the method is good enough to permit one to follow the different steps in the conversion of porcine insulin to human insulin.     

Quantitative molecular approach to the permeability changes of excitation

Functional relationships, available from only a few monolayer studies, can be applied to a relatively simple model of the excitable membrane to give permeability-potential curves quite similar to the conductance-potential curves obtained experimentally in voltage-clamped giant axons. Contrary to the usual view in terms of "carrier systems," the present model considers the permeability to sodium and potassium to be reduced by the increase in the surface pressure induced by large lipophilic cations and anions in the outer layer of the lipoidal bimolecular leaflet constituting the living membrane; hence, the increase in permeability during depolarization, for example, is due to a decrease in the amount of the organic anions in this layer, whereas the decrease in sodium permeability during inactivation is caused by a rise in content of organic cations. The present proposal has the advantage that it is in keeping with known phenomena observed in simple physico-chemical systems as well as in excitable systems; moreover, the current actually transferred by the postulated lipophilic ions can be negligible compared to that transferred by the inorganic cations they control. The latter situation, as well as the steepness of the permeability-potential relationships obtained, have been pointed out to be critical requirements of a satisfactory molecular hypothesis.     

拟南芥中类黄酮代谢途径及其调控

综述黄酮类化合物的重要生物学作用,类黄酮代谢的合成、关键酶、转运途径,以及代谢调控因子等方面的研究现状与进展。     

Taming superacids: stabilization of the fullerene cations HC60+ and C60.+

A new superacid, H(CB11H6X6) (where X = chlorine or bromine), whose conjugate base is the exceptionally inert CB11H6X6- carborane anion, separates Bronsted acidity from oxidizing capacity and anion nucleophilicity in a manner not previously achieved. Reaction of this superacid with C60 gives HC60+ as a stable ion in solution and in the solid state. In a separate experiment, an oxidant was developed such that the long-sought C60.+ ion can be synthesized in solution. The preparation of these two fullerene carbocations is a notable departure from the prevalent chemistry of C60, which is dominated by the formation of anions or the addition of nucleophiles. The H(CB11H6X6) superacid overcomes the major limitations of presently known superacids and has potentially wide application.     

Voltage-dependent calcium channels from Paramecium cilia incorporated into planar lipid bilayers

Two different divalent cation-selective channels from Paramecium cilia were incorporated into planar lipid bilayers. Both channels were much more permeable to divalent than univalent cations, and one of them discriminated significantly among the divalent cations. The selectivity and voltage dependence of the latter channel are comparable to those of voltage-dependent calcium channels found in a variety of cells. A combined biochemical, biophysical, and genetic study of calcium channels is now possible.     

Strontium accumulation by sarcoplasmic reticulum and mitochondria in vascular smooth muscle

Electron-opaque deposits of strontium were observed in the sarcoplasmic reticulum and in mitochondria of spontaneously contracting vascular smooth muscles that had been incubated in a strontium-containing solution prior to fixation. The deposits were present in those elements of the sarcoplasmic reticulum that are in close contact with the surface membrane and also in more centrally located portions. In vascular smooth muscle that does not contract spontaneously, similar deposits of strontium were only seen if the muscle was depolarized during or glycerinated before exposure to the strontium-containing solution. Strontium was also deposited in the sarcoplasmic reticulum of the endothelium. It is suggested that translocation of calcium from the sarcoplasmic reticulum that is in close contact with the surface membrane, and now shown to accumulate divalent cations, is responsible for the action potential-triggered contractions of rabbit and guinea pig mesenteric veins. Strontium may also be a suitable marker for identifying sites that accumulate calcium in other types of cells in which translocation of calcium plays a major regulatory function.     

瓜环家族新成员——半瓜环超分子化学研究进展

本文总结了一类新型大环化合物--半瓜环的发展历程,包括半瓜环的合成及结构特点;半瓜环与金属离子、阴离子及小分子主客体作用;半瓜环在超分子催化中的应用及底物结构对其催化性能的影响;新型半瓜环,例如环己基半瓜环和竹节半瓜环的合成及其超分子化学性质;作为一种新型的大环化合物,半瓜环的研究目前处于起步阶段,在超分子化学的基础研究及相关的应用研究方面有着广阔的前景.     

Mesostructure design with gemini surfactants: supercage formation in a three-dimensional hexagonal array

At low temperatures, liquid crystal-like arrays made up of inorganic-cluster and organic molecular units readily undergo reversible lyotropic transformations. Gemini surfactants, with two quaternary ammonium head groups separated by a methylene chain of variable length and with each head group attached to a hydrophobic tail, can be used to control organic charge sitting relative to the bivariable hydrophobic tail configurations. This approach has led to the synthesis of a mesophase (SBA-2) that has three-dimensional hexagonal (P6(3)/mmc) symmetry, regular supercages that can be dimensionally tailored, and a large inner surface area. This mesostructure analog of a zeolite cage structure does not appear to have a lyotropic surfactant or lipid liquid crystal mesophase counterpart. Through the modification of gemini charge separation and each of the two organic tails, these syntheses can be used to optimize templating effects, including the synthesis of MCM-48 at room temperature.     

Chemistry. Superacids--it's al lot about anions

Superacids are powerful agents for protonating weak bases, with applications ranging from synthetic chemistry to batteries and fuel cells. DesMarteau explains in his Perspective that many superacids have undesirable properties, because after proton donation, the resulting anion may interact strongly with the protonated base or the solvent. Reed et al. report the discovery of a superacid that overcomes this problem. In the anion, charge is distributed efficiently over many atoms, reducing unwanted interactions.     

福寿螺在昭平的发生趋势及综防对策

福寿螺是过去因无知而作为有益生物引进我区养殖,由于缺乏有效控制,现已成为危害昭平县水稻及多种作物的有害生物,在一些乡镇的稻田中,螺口密度达9.5~40.6只/m2。2005年全县受螺害的水稻面积达6728.2hm2,占全县水田种植面积的62.3%。必须在政府或村委会有计划的组织下,采取村屯联防的方式,才能彻底防治螺害。     

Ion binding by synthetic macrocyclic compounds

The existence of synthetic macrocyclic molecules with hydrophilic cavities containing multiple binding atoms and with hydrophobic exteriors gives rise to extraordinary possibilities with respect to the design and synthesis of molecules with specific cation and anion binding properties. The preparation of many new macrocyclic compounds has recently been reported, but few practical applications for them have been suggested. From the information available, it is becoming clear that it should be possible to synthesize macrocycles that will have specified, or selected, ion binding properties. Cavity size can be varied to accommodate only those cations or anions within a specified narrow band of sizes. Numbers and types of coordinating atoms can be chosen to give essentially electrostatic or covalent bonding or a combination of the two in a metalmacrocycle complex. The metal ligand bond appears to be predominantly ionic in the case of the cyclic polyethers but the covalent character increases on substitution of sulfur or nitrogen for oxygen donor atoms. The essential hydrophobic exteriors of the macrocycles can be modified by the addition of side chains and groups to facilitate the solution of anions and cations in organic solvents. The structures of many macrocycles can be made to approximate naturally occurring molecules, that is, cyclic polyethers similar to macrocyclic antibiotics of the valinomycin and nonactin types and cyclic polyamines similar to porphyrins. Macrocycles are also useful as model compounds for the study of metal interactions with biological systems. The synthetic macrocycles thus represent an intriguing new area of coordination chemistry, the systematic study of which should lead to many interesting and useful chemical applications in the field of metal complexation in solution.     

Target-oriented and diversity-oriented organic synthesis in drug discovery

Modern drug discovery often involves screening small molecules for their ability to bind to a preselected protein target. Target-oriented syntheses of these small molecules, individually or as collections (focused libraries), can be planned effectively with retrosynthetic analysis. Drug discovery can also involve screening small molecules for their ability to modulate a biological pathway in cells or organisms, without regard for any particular protein target. This process is likely to benefit in the future from an evolving forward analysis of synthetic pathways, used in diversity-oriented synthesis, that leads to structurally complex and diverse small molecules. One goal of diversity-oriented syntheses is to synthesize efficiently a collection of small molecules capable of perturbing any disease-related biological pathway, leading eventually to the identification of therapeutic protein targets capable of being modulated by small molecules. Several synthetic planning principles for diversity-oriented synthesis and their role in the drug discovery process are presented in this review.     

电渗析法研究紫色土、黄壤和砖红壤的酸化特征

【目的】研究紫色土、黄壤和砖红壤在快速酸化过程中的酸化特征。【方法】将3种供试土壤在15 V·cm^-1的外加直流电压梯度下进行连续30次,每次8 h的电渗析。并通过测定电渗析前后土壤的酸度指标、盐基离子含量以及在电渗析过程中土壤所释放的盐基离子含量来分析土壤的酸化特征。【结果】电渗析法可在短时间内实现土壤的快速酸化,3种土壤的pH均降低至4.5以下的强酸化水平。电渗析后,3种土壤的交换性酸、交换性H⁺和交换性Al³⁺含量显著增加。紫色土、黄壤和砖红壤的交换性酸含量分别从3.35、0.23和0.76 cmol(+)·kg^-1增加至18.9、7.0和5.8 cmol(+)·kg^-1,可见紫色土的酸化程度最为严重。土壤酸化后,水溶性和交换性K⁺、Na⁺、Ca²⁺和Mg²⁺含量降低,其中Ca²⁺、Mg²⁺的降低幅度较大。酸化导致土壤的交换性盐基总量和盐基饱和度下降,紫色土、黄壤和砖红壤的盐基饱和度从电渗析前的96.8%、82.6%和47.3%降低至电渗析后的20.5%、11.8%和12.2%。尽管紫色土的交换性酸含量远大于黄壤和砖红壤,但交换性盐基离子总量和盐基饱和度也大于黄壤和砖红壤。由于各土壤的交换性Ca²⁺和Mg²⁺含量大于交换性K⁺和Na^＋含量,且相对于K⁺和Na^＋,Ca²⁺和Mg²⁺与带负电的土壤颗粒间具有更强的静电引力,因此在酸化过程中,一价盐基离子K⁺和Na^＋在3种土壤中均表现为快速释放,而二价盐基离子Ca²⁺和Mg²⁺表现出缓慢释放和波动释放的规律。3种供试土壤,随着土壤发育程度增加,土壤的潜在酸化风险下降（紫色土>黄壤>砖红壤）,但土壤的盐基饱和度表现出紫色土>黄壤≈砖红壤。可以看出,紫色土的酸化特征表现出这种明显的“双面性”,由于紫色土具有较高的CEC值,导致土壤酸化后的交换性酸含量显著高于黄壤和砖红壤,使酸化紫色土上生长的植物存在较高的铝毒害风险;同时,由于紫色土丰富的矿物组分能够对盐基离子进行及时补充,紫色土酸化后仍含有相对较高的盐基离子含量和盐基饱和度,保证了植物生长对盐基养分离子需求,也能在一定程度上缓解紫色土的进一步酸化。【结论】电渗析法可用于模拟土壤的快速酸化过程;土壤的表面负电荷量和复盐基离子能力是决定土壤酸化特征的关键因素;紫色土具有异于地带性土壤黄壤和砖红壤的“双面性”酸化特征。     

Intercalated clay catalysts

Recent advances in the intercalation of metal complex cations in smectite clay minerals are leading to the development of new classes of selective heterogeneous catalysts. The selectivity of both metal-catalyzed and proton-catalyzed chemical conversions in clay intercalates can often be regulated by controlling surface chemical equilibria, interlamellar swelling, or reactant pair proximity in the interlayer regions. Also, the intercalation of polynuclear hydroxy metal cations and metal cluster cations in smectites affords new pillared clay catalysts with pore sizes that can be made larger than those of conventional zeolite catalysts.     

The mechanism of DNA transfer in the mating system of an archaebacterium

The genetic transfer system in the extremely halophilic archaebacterium Halobacterium volcanii is the only archaebacterial mating system known. The mechanism of genetic transfer of this archaebacterium was studied by using the immobile plasmids pHV2 and pHV11 as cytoplasmic markers. It was found that the cytoplasms of the parental types do not mix during the mating process, that each parental type can serve both as a donor and as a recipient, and that cytoplasmic bridges, with dimensions of up to 2 micrometers long and 0.1 micrometer in diameter, were formed between the parental types. These bridges appear to be used for the transfer of DNA from one cell to another. If so, this archaebacterial mating system is different from both eubacterial conjugation and eukaryotic sexual cell fusion.     

地塞米松与肝素对HL－60细胞增值和生物大分子合成的影响

用地塞米松（Ｄｅｘ）和肝素（Ｈｅｐ）Ｉｃ６０及Ｉｃ５０低一个剂量，对ＨＬ－６０细胞增殖、生长曲线和分裂指数均有明显的抑制作用，联合应用时抑制作用显著增强；对ＤＮＡ和蛋白质合成抑制作用大于ＲＮＡ，联合应用抑制作用均显著增强，提示两药抑制ＨＬ－６０细胞增殖、分裂和生长可能与它们抑制ＤＮＡ和蛋白质合成有关，亦与抑制ＲＮＡ合成有一定关系。     

消雷器能不能消雷

介绍了消雷器消雷的理论依据－－“中和理论”及消雷器消雷失败的实例，了消雷器消雷的关键是消雷器在雷云电场作用下产生的电晕电流能否“中和”雷云中的电荷。通过采用多针导何体消雷器和避雷器对比方法测量电晕电流，对其结果进行消雷可能性分析，得出结论：一般雷云携带电荷量约２０－１００℃，依靠消雷器释放的电荷“中和”２０Ｃ雷云电荷需８０ｈ，而雷云移过建筑物的时间只有２．７ｍｉｎ，因此仅在２．７ｍｉｎ内消雷器不能     

铁·镁·钙元素对白腐真菌生长及降解石油的影响

[目的]探讨黄孢原毛平革菌的生长及对石油的降解能力的优化条件。[方法]选用白腐真菌的典型菌种——黄孢原毛平革菌作为降解菌,研究其生长及对石油的降解性能,以不同浓度的Fe、Mg、Ca元素作为研究对象,在筛选单因素最佳水平的基础上,设计L9(33)正交表进行正交试验,对各因素的重要性及其最优水平进行分析。[结果]单因素试验表明,体系中添加Fe、Mg、Ca元素对白腐真菌的生长及其对石油的降解能力有较大的影响。正交试验结果表明,3种元素对P.C.菌降解石油的影响大小依次为Fe2+Ca2+Mg2+;溶液中铁、镁、钙元素的最佳组合为0.008 g/L的Fe2+、0.8 g/L的Mg2+、1.5 g/L的Ca2+,该条件下10 d后白腐真菌对石油的降解率为70.9%。[结论]该研究为探索白腐真菌的生长及其对石油降解能力的优化提供了科学依据。