Supramolecular Archimedean cages assembled with 72 hydrogen bonds

Self-assembly of multiple components into well-defined and predictable structures remains one of the foremost challenges in chemistry. Here, we report on the rational design of a supramolecular cage assembled from 20 ions of three distinct species through 72 hydrogen bonds. The cage is constructed from two kinds of hexagonal molecular tiles, a tris(guanidinium)nitrate cluster and a hexa(4-sulfonatophenyl)benzene, joined at their edges through complementary and metrically matched N-H···O-S hydrogen bonds to form a truncated octahedron, one of the Archimedean polyhedra. The truncated octahedron, with an interior volume of 2200 cubic angstroms, serves as the composite building unit of a body-centered cubic zeolite-like framework, which exhibits an ability to encapsulate a wide range of differently charged species, including organic molecules, transition metal complexes, and "ship-in-a-bottle" nanoclusters not observed otherwise.     

锰离子胁迫下外生菌根真菌对土壤钾释放的影响

外生菌根真菌作为森林生态系统的组成部分,参与植物的养分吸收和利用。试验以彩色豆马勃(Pisolithus tinctorius,Pt)和松乳菇(Lactarius deliciosus,Ld)作为供试菌株,以土壤作为培养基唯一钾源,采用液体培养的方法,研究不同锰离子质量浓度下2株供试菌株活化土壤难溶性钾的能力与机理。结果显示,2株外生菌根真菌的生物量随锰离子质量浓度升高而减低,生长受到显著(P<0.05)抑制。在相同锰离子质量浓度下,菌株Pt的菌丝生物量均大于Ld,说明Pt的抗锰能力强于Ld。2株外生菌根真菌均分泌草酸和乙酸,培养基中的pH下降。同时,2株外生菌根真菌均能降低土壤中矿物结构钾的含量,并增加土壤中交换性钾含量,说明在锰离子胁迫下,外生菌根真菌能活化土壤中的难溶性钾。相关分析表明,培养液中草酸分泌量与土壤交换性钾含量呈极显著(P<0.01)正相关,与土壤矿物结构钾含量呈显著(P<0.05)负相关,培养基中的pH与土壤中交换性钾含量呈极显著(P<0.01)负相关。推测外生菌根真菌分泌的有机酸和氢离子有利于土壤难溶性钾的活化,其中草酸可能起到关键作用。由于有机酸和氢离子的分泌量不同,2株外生菌根真菌对土壤难溶性钾的活化能力存在差异。     

Transformation of gibbsite to chlorite in ocean bottom sediments

Numerous grains of gibbsite surrounded by zones of chlorite were found in six samples of sediment taken from Waimea Bay off the coast of Kauai, Hawaii. The chlorite has formed from the gibbsite, and growth bands in the chlorite either are parallel to chlorite-gibbsite interfaces or are concentric around small remnants of gibbsite. Aggregates were found that appeared to be composed of two or more gibbsite grains surrounded by chlorite bands that have grown together. The index of refraction of the chlorite ranged from 1.58 to 1.60 and the chlorite displayed anomalous blue interference colors. The gibbsite was formed on land under conditions of strong weathering and strong leaching. When transported to the sea, the gibbsite was deposited in a solution containing silicic acid, magnesium, potassium, and hydrogen ions, in which it is unstable. Chlorite, a stable mineral in this solution, replaced the gibbsite.     

Scroll-shaped waves of chemical activity in three dimensions

Ferric ions catalyze the oxidation of malonate by bromate in acid solution, sometimes at a spatially uniform, steady rate, but sometimes in a self-regenerating three-dimensional wave which resembles a rotating scroll, often with its axis closed in a ring. In cross section perpendicular to the axis, one sees an involute spiral emerging from a thin cylindrical core. This "dissipative structure" organizes reaction stages periodically in space and time everywhere except along its rotation axis, which may therefore be a thermodynamically unique locus.     

Autoionization in liquid water

The dissociation of a water molecule in liquid water is the fundamental event in acid-base chemistry, determining the pH of water. Because of the short time scales and microscopic length scales involved, the dynamics of this autoionization have not been directly probed by experiment. Here, the autoionization mechanism is revealed by sampling and analyzing ab initio molecular dynamics trajectories. We identify the rare fluctuations in solvation energies that destabilize an oxygen-hydrogen bond. Through the transfer of protons along a hydrogen bond "wire," the nascent ions separate by three or more neighbors. If the hydrogen bond wire connecting the two ions is subsequently broken, a metastable charge-separated state is visited. The ions may then diffuse to large separations. If, however, the hydrogen bond wire remains unbroken, the ions recombine rapidly. Because of their concomitant large electric fields, the transient ionic species produced in this case may provide an experimentally detectable signal of the dynamics we report.     

Isolating the spectroscopic signature of a hydration shell with the use of clusters: superoxide tetrahydrate

Cluster spectroscopy, aided by ab initio theory, was used to determine the detailed structure of a complete hydration shell around an anion. Infrared spectra of size-selected O(2)-. (H(2)O)(n) (n = 1 to 4) cluster ions were obtained by photoevaporation of an argon nanomatrix. Four water molecules are required to complete the coordination shell. The simple spectrum of the tetrahydrate reveals a structure in which each water molecule is engaged in a single hydrogen bond to one of the four lobes of the pi* orbital of the superoxide, whereas the water molecules bind together in pairs. This illustrates how water networks deform upon accommodating a solute ion to create a distinct supramolecular species.     

Mutations affecting internal TEA blockade identify the probable pore-forming region of a K+ channel

The active site of voltage-activated potassium channels is a transmembrane aqueous pore that permits ions to permeate the cell membrane in a rapid yet highly selective manner. A useful probe for the pore of potassium-selective channels is the organic ion tetraethylammonium (TEA), which binds with millimolar affinity to the intracellular opening of the pore and blocks potassium current. In the potassium channel encoded by the Drosophila Shaker gene, an amino acid residue that specifically affects the affinity for intracellular TEA has now been identified by site-directed mutagenesis. This residue is in the middle of a conserved stretch of 18 amino acids that separates two locations that are both near the external opening of the pore. These findings suggest that this conserved region is intimately involved in the formation of the ion conduction pore of voltage-activated potassium channels. Further, a stretch of only eight amino acid residues must traverse 80 percent of the transmembrane electric potential difference.     

Cytidylic acid "a" trihydrate: structure and conformation

Cytidylic acid "a" (cytidine 2'-monophosphate) crystallizes in the triclinic space group P1 with two molecules of cytidine monophosphate (C(9)H(14)O(8)N(3)P) and six molecules of water in the unit cell. X-ray analysis of this crystal shows that in both molecules, the base is in the anti conformation, the ribose ring is C(2')-endo puckered, and the hydroxyl O(5') is gauche-gauche. The two molecules are linked by a short hydrogen bond through the phosphate oxygens.     

Reversible cleavage and ligation of hepatitis delta virus RNA

A 148-nucleotide subfragment of hepatitis delta virus RNA was shown to undergo cleavage and ligation reversibly. The direction of the reaction is determined by the presence or absence of Mg2+ ions, with the presence of Mg2+ favoring the cleavage reaction. Ligation requires specific conformation of the RNA molecules involved and occurs only between two cleaved RNA fragments that are still held together by hydrogen bonds. The ligation reaction occurs rapidly on removal of Mg2+ by EDTA. This represents a new class of RNA enzymes.     

Structure of a glycerol-conducting channel and the basis for its selectivity

Membrane channel proteins of the aquaporin family are highly selective for permeation of specific small molecules, with absolute exclusion of ions and charged solutes and without dissipation of the electrochemical potential across the cell membrane. We report the crystal structure of the Escherichia coli glycerol facilitator (GlpF) with its primary permeant substrate glycerol at 2.2 angstrom resolution. Glycerol molecules line up in an amphipathic channel in single file. In the narrow selectivity filter of the channel the glycerol alkyl backbone is wedged against a hydrophobic corner, and successive hydroxyl groups form hydrogen bonds with a pair of acceptor, and donor atoms. Two conserved aspartic acid-proline-alanine motifs form a key interface between two gene-duplicated segments that each encode three-and-one-half membrane-spanning helices around the channel. This structure elucidates the mechanism of selective permeability for linear carbohydrates and suggests how ions and water are excluded.     

混合络合物的形成及生物学意义

自然界特别是在生物体系中广泛地存在着混合型络合物。它的形成可以是一步同时生成或逐步生成,也可以是由单一型络合物混合生成。混合络合物的稳定性是由如下因素所决定的,即:统计效应,静电效应,共价键性,立体效应和配体的合作效应。在生物体内,混合络合物的形成涉及到:生物分子的稳定化和三维构象的稳定化,金属离子和配体分子的分布和运转,某些金属酶的催化作用(如脱羧酶、水解酶,羰基水化酶,碳酸酐酶等)及生物固氮等等问题。     

超声波辐射合成香豆素-3-甲酸乙酯

[目的]利用超声波辐射技术合成香豆素-3-甲酸乙酯,并优化其反应条件。[方法]采用超声波辐射技术,经Knoevenagel缩合反应合成了香豆素-3-甲酸乙酯,产物经IR1、HNMR表征。通过单因素优选法研究了不同水杨醛和丙二酸二乙酯投料比例、反应温度、辐射时间、无水乙醇用量、六氢吡啶用量对反应产率的影响。[结果]超声波辐射法制备香豆素-3-甲酸乙酯的最佳合成条件：水杨醛与丙二酸二乙酯物质的量之比为1.001∶.30,无水乙醇25 ml,六氢吡啶0.5 ml,在65℃下,超声波辐射作用80 min,产率达97.46%。[结论]与传统法相比,该合成方法缩短了反应时间,较常规方法产率提高了近20个百分点。     

Composition measurements of the topside ionosphere

Data from a magnetic mass spectrometer flown on the Explorer 31 satellite show that the ionosphere above 1000 kilometers usually consists of hydrogen ions as the predominant species. Between this altitude and perigee (500 kilometers) the dominant ion species shifts to atomic oxygen, with a significant amount of atomic nitrogen ions also present. Helium ions are present in small quantities at all altitudes. Other minor ions observed are those of 2, 7, 8, 15, 18, and 20 atomic mass units.     

湿地植物根系分泌物中有机酸对NSAIDs胁迫的响应

以人工湿地典型植物芦苇（Phragmites australis）为研究对象,探索芦苇根系分泌物中有机酸对非甾体类消炎药（NSAIDs）混合物（双氯芬酸、布洛芬、吲哚美辛、酮洛芬、萘普生）长期胁迫的响应。首先,优化测定有机酸的高效液相色谱（HPLC）法;然后,构建水培和人工湿地两种体系,于NSAIDs胁迫下（地表水浓度...     

稀土离子与均苯三甲酸配位稳定性研究

利用高锰酸钾氧化1,3,5-三甲苯制备了均苯三甲酸（苯-1,3,5-三甲酸）,经纯化后,在（25±0.1）℃及离子强度I=0.1 mol·L-1KNO3条件下,用电位滴定法测定了均苯三甲酸的纯度及稀土离子与均苯三甲酸配位稳定常数,lgKML对稀土元素的原子序数显示了“双－双”效应,这对稀土离子的分离提纯提供了一种新的可能性。     

KF/Al2O3合成香豆素-3-羧酸的工艺研究

以水杨醛、丙二酸二乙酯为原料,KF/Al2O3为催化剂合成了香豆素-3-羧酸乙酯,产物不经分离,直接进行皂化、酸解环合制备香豆素-3-羧酸。采用元素分析、熔点测定、红外光谱（IR）等手段对中间体和产物进行了结构表征。考察了各反应条件对香豆素-3-羧酸收率的影响,确定了最佳工艺条件为：水杨醛4.0g（0.033mol）,水杨醛和丙二酸二乙酯物质量比为1.0∶1.2,反应时间100min,香豆素-3-羧酸的收率〉85%。     

烟台高新区沿海土壤理化分析

为给沿海区土壤高效、合理地利用与管理提供参考依据,针对烟台高新区沿海土壤理化性质进行分析。结果表明:烟台高新区土壤p H均在6.3~7.0,呈弱酸性到中性;全盐量在0.049%~0.460%,大部分土壤样品全盐量小于0.200%,属于轻度盐渍化;全盐量(Y)与电导率(X)的二次曲线回归方程:Y=0.052X~2+0.186X+0.048,两者决定系数R~2=0.999,根据二次曲线方程用电导率值计算所得的土壤全盐量与质量法实测的全盐量之间的相对误差多在5%以下;钠离子含量是钾离子的2~10倍,经SPSS 20.0相关性分析,钾、钠离子含量及两者总量与全盐量之间均呈现极显著正相关。     

Mutations affecting TEA blockade and ion permeation in voltage-activated K+ channels

Voltage-dependent ion channels are responsible for electrical signaling in neurons and other cells. The main classes of voltage-dependent channels (sodium-, calcium-, and potassium-selective channels) have closely related molecular structures. For one member of this superfamily, the transiently voltage-activated Shaker H4 potassium channel, specific amino acid residues have now been identified that affect channel blockade by the small ion tetraethylammonium, as well as the conduction of ions through the pore. Furthermore, variation at one of these amino acid positions among naturally occurring potassium channels may account for most of their differences in sensitivity to tetraethylammonium.     

Multiplex spectroscopy: determining the transition moments and absolute concentrations of molecular species

A procedure is described that uses two spectroscopic techniques, absorption and infrared degenerate four-wave mixing, in tandem (multiplex) to measure the transition dipole moments and absolute concentrations of molecular species in situ. The method is demonstrated by the measurement of the relative transition moments and concentrations of two dissimilar sample gas components, hydrogen chloride and nitrogen dioxide, but is applicable to a wide variety of molecules and, thus, can provide new information for transient molecular species. Further, difficulties in obtaining quantitative information through techniques such as laser-induced fluorescence, coherent anti-Stokes Raman scattering, and degenerate four-wave mixing spectroscopies can be overcome when a multiplex approach is used.     

The preparation and structures of hydrogen ordered phases of ice

Two hydrogen ordered phases of ice were prepared by cooling the hydrogen disordered ices V and XII under pressure. Previous attempts to unlock the geometrical frustration in hydrogen-bonded structures have focused on doping with potassium hydroxide and have had success in partially increasing the hydrogen ordering in hexagonal ice I (ice Ih). By doping ices V and XII with hydrochloric acid, we have prepared ice XIII and ice XIV, and we analyzed their structures by powder neutron diffraction. The use of hydrogen chloride to release geometrical frustration opens up the possibility of completing the phase diagram of ice.