Phosphorus within planetary boundaries

ABSTRACT

In this paper the screening calculations of the removal time of phosphorus from water bodies of federal districts of Russia are presented. Calculations are made using the matrix algebra based approach and are applied as a tool for the estimation of the fate of phosphates in different environmental media (water, air, soil, biota, etc.). The results show that the use of phosphate fertilizers is sometimes quite high in the most vulnerable federal districts. It means that the application of fertilizers in order to increase the yield of agriproducts should be accompanied by detailed assessment of the risks of eutrophication. Calculations have shown high vulnerability in the district of the Lake Baika.     

Chiral photochemistry within zeolites

Chiral induction of chemical reactions continues to be one of the main concerns of chemists. While basic rules of chiral induction of thermal reactions have been reasonably established, the same is not true of photochemical reactions. Short excited state lifetime and low activation energies for reactions in the excited state(s) leave very little room for manipulating the diastereomeric transition states. Yet impressive chiral induction of photochemical reactions in the solid state has been achieved. On the other hand, chiral induction of photoreactions of organic molecules in solution continues to be inefficient at ambient conditions. We are exploring the possibility of employing zeolites as a media for achieving chiral induction during photoreactions. The motivating force for such an attempt is the fact that chiral chemistry in the solid state is not completely general due to the fact that not all molecules crystallize. To achieve chiral induction one needs a chiral perturber. Zeolites are not chiral and therefore the perturber is added to the medium. Thus the medium for a photoreaction is a chirally modified zeolite. Of the several reactions investigated, results on photoelectrocylization of tropolone alkyl ethers are discussed at length. The confined space offered by the zeolite supercage forces a reactant and the chiral inductor to interact intimately to yield enantiomerically enriched product. Due to the transitory nature of the reaction cavity in solution such close interactions are less likely in isotropic solvent media. The examples discussed herein show negligible chiral induction in solution, whereas in a zeolite one obtains induction as high as 90%.     

Quality and quantity within medicine

The concept of quality is placed both within a historical as well as philosophical light. It is argued that nowadays general and laboratory medicine is a logical extension of economical and social concepts which stem from the beginning of the twentieth century. However, it seems that medicine cannot be explained based entirely upon these concepts. The medical field has a variety of definitions of quality: all depending on the person and/or institution posing the questions. The quality concept sometimes concerns an individual and sometimes a group of individuals. The quality definition and indicator scores are then different. This quantified quality can also be looked upon from an eastern (i.e. Japanese, Chinese, ancient Greece) perspective. The ideal world, framed within a cyclic evaluation between well-defined static situations, does not relate easily with the individualized (quantified quality) western medical world. Nevertheless, we are in search of a quality concept that balances the western industrial model of medicine and the eastern, philosophical approach. Papers published in this section do not necessarily reflect the opinion of the Editors, the Editorial Board and the Publisher. Apart from exceptional circumstances, they are not submitted to the usual referee procedure and go essentially unaltered. Presented at the European Conference on Quality in the Spotlight in Medical Laboratories, 7–9 October 2001, Antwerp, Belgium     

金属硫蛋白家族内的结构域拼接

金属硫蛋白(Metallothioneins,MTs)由结构独立且功能明显区别的β,α两个结构域组成。神经生长抑制因子(NeuronalGrowthInhibitoryFactor,GIF)双名金属硫蛋白-Ⅲ(MT-Ⅲ),是神经系统中第一个被鉴定的具有神经元生长抑制功能的蛋白,而β－结构域为其功能结构域。为深入系统地研究MTs,尤其是GIF及其结构域的结构与功能,我们构建了金属硫蛋白家族内结构域拼接体βGIF-αMT-1(βⅢ-αⅠ)和βMT-1-αGIF(βⅠ-αⅢ):PCR扩增得各个结构域的cDNA序列,酶切后克隆入原核表达载体pGEX-4T-1,经发酵、诱导表达、亲和层析、凝血酶切和进一步纯化,得率约为80mg蛋白/L菌液。测其电泳行为、氨基酸组成、质谱、金属巯基含量等,证明得到了目的蛋白。紫外吸收图谱和圆二色性图谱显示,结构域拼接体拥有金属硫蛋白家族成员的特征金属巯基簇结构域,初步功能实验表明,βⅢ－αⅠ也具有抑制神经元生长的功能。     

Electrodeposition within zeolite membrane hosts

An electrochemical procedure for the incorporation of metal nanoparticles (diameter ∼1 nm) into coherent zeolite membranes is reported. The method is exemplified with the deposition of platinum in healed zeolite Y membranes but has also been applied to copper deposition within membranes of silicalite.     

Controlling porosity within colloidal heteroaggregates

Heteroaggregates of cationic poly(2-vinylpyridine) microgels and anionic polystyrene latex particles have been made by mixing dilute, aqueous suspensions. The growth of the heteroaggregates was arrested by the addition of anionic silica particles that adsorbed to the free surface of the cationic microgel particles. The resulting heteroaggregates were then concentrated by vacuum filtration, freeze-dried, and characterized by mercury porosimetry and electron microscopy. The inclusion of soft, deformable microgels resulted in heteroaggregates with higher porosity than obtained with heteroaggregates of anionic and cationic latex particles. Control of the pore volumes within the freeze-dried filter cakes was demonstrated by two approaches. In the first approach, heteroaggregation at a constant KCl concentration of 0.01 mM was arrested at different times after mixing the latex and microgel particles, thereby limiting the size of the aggregates. The porosity of the resulting filter cake increased from 61 to 65 vol % as the aggregation time increased from 15 to 120 s. In the second technique, the aggregation time prior to arrest was maintained at 120 s while the KCl concentration was varied between 0.01 and 10 mM. The pore volume of the aggregates decreased from 65 to 57 vol % as the electrolyte concentration increased, a trend explained in terms of the effect of the Debye length on the aggregation process.     

Structural-chemical evolution within exfoliated clays

The exfoliated (delaminated) structures of lamellar clays offer potential as precursors for the formation of various nanostructured materials. In this article, Lucentite and Laponite phyllosilicate clays, which both have empirical formulas of Na(0.33)[Mg(2.67)Li(0.33)Si4O10(OH)2] but differ in nanodimensions, have been exfoliated. Experiments were carried out for mixtures containing approximately 1 wt % phyllosilicate in a 5% aqueous solution of poly(acrylic acid) at different temperatures. X-ray diffraction and photoemission spectroscopy measurements for the solid products recovered after stirring the mixtures at 20 degrees C showed that the fully extended chains of poly(acrylic acid) were intercalated within the interlayer spaces between the silicate plates of the clays. At 85 degrees C, however, the clays were exfoliated and/or partially exfoliated. Photoemission spectroscopy also indicated that the exfoliated structures primarily consisted of silica nanoplates. 29Si nuclear magnetic resonance and oxygen K-edge near-edge X-ray absorption fine structure indicated that the surfaces of the plates were terminated by high concentrations of the silanol (-SiOH) groups, which created structural branches during intercalation. A model was developed in which intercalation and the removal of ions from the clays after the poly(acrylic acid) interactions reduced the electrostatic van der Waals forces between the plates. It was also shown that the formation of branches created a steric effect that inhibited the stacking of the plates. Together these resulted in exfoliation.     

Induced reaction within the peroxy-compounds

Summary The induced reaction occurring in the H₂O₂-H₂S₂O₈- KMnO₄ [and Ce(SO₄)₂, resp.,] system was studied in detail and established that it strongly depends on the experimental conditions such as rate of stirring, speed of titration, dilution of the solution, temperature, concentrations of partners of the reaction, acid concentration etc. It was found further that the induced disappearence of peroxydisulphate as well as of hydrogen peroxide is caused by HO₂ radicals formed during the primary reaction between hydrogen peroxide and 1-equivalent oxidants. The effect of foreign ions on the induced reaction was also interpreted.

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Zusammenfassung Die induzierte Reaktion im System H₂O₂-H₂S₂O₈-KMnO₄ bzw. Ce(SO₄)₂ wurde eingehend untersucht und gefunden, daß sie weitgehend von den Versuchsbedingungen abhängig ist (Rühr- und Titrier-geschwindigkeit, Verdünnungsgrad, Temperatur, Konzentration der Reaktionspartner, Säurekonzentration u. a.). Das Verschwinden von Peroxydisulfat und Wasserstoffperoxid bei der induzierten Reaktion wird durch HO₂-Radikale verursacht, die während der induzierenden Reaktion zwischen Wasserstoffperoxid und 1-äquivalenten Oxydations mitteln gebildet werden. Die Wirkung von Fremdionen auf die induzierte Reaktion wird ebenfalls erläutert.

     

Sieving transport within wavy-rough nanoannuli

We demonstrate the molecular sieving could be realized via a wavy-rough nanoannulus. By using the boundary perturbation method, we analytically obtain the flow rate (up to the second order) inside the wavy-rough nanoannuli. Our results show that for smaller forcing (along the nanoannulus-axis direction) there are significantly different flow rates for different amplitudes of wavy-roughness. This implies the fine-tuning of the solid-fluid interface of nanoannuli could be an efficient way for the molecular sieving.     

Molecular aggregation within self-ordered monolayers.

The monolayer growth of pyrimido-pentaphenylbenzene (NPB) on Cu(111) is investigated by means of low-temperature scanning tunneling microscopy (LT-STM). The pyrimidine side group gives rise to a pronounced resonant tunneling state and, furthermore, affects molecular self-ordering. Different molecular aggregates are formed inside the hexagonal closed packed monolayer. A structure model for the monolayer is proposed and the temperature dependence of this self-ordering process is investigated by varying the preparation temperature between 270 and 370 K. The intermolecular bonding of the aggregates is demonstrated by STM manipulation experiments. Moreover, different aggregations of the molecules induce characteristic energy shifts in the resonant tunneling state, as revealed by means of scanning tunneling spectroscopy.     

微反应器中的不对称光化学反应

化学反应的手性诱导一直备受化学家的关注,虽然不对称热化学合成和手性技术已经取得了巨大的进展,但不对称光化学反应的研究远远没有取得相应的成功.激发态寿命短、活化能低是导致其对映选择性低的主要原因.最新的研究表明,采用含手性空间或经手性修饰的微环境可以使光化学反应的立体选择性大大提高.本文针对这一热点问题,综述在微反应器中进行不对称光化学反应的研究进展.     

Oxygen vacancy ordering within anion-deficient Ceria

The structural properties of anion deficient ceria, CeO_2−δ, have been studied as a function of oxygen partial pressure, p(O₂), over the range 0≥log₁₀ p(O₂)≥−18.9 at 1273(2) K using the neutron powder diffraction technique. Rietveld refinement of the diffraction data collected on decreasing p(O₂) showed increases in the cubic lattice parameter, a, the oxygen nonstoichiometry, δ, and the isotropic thermal vibration parameters, u_Ce and u_O, starting at log₁₀ p(O₂)~−11. The increases are continuous, but show a distinct kink at log₁₀ p(O₂)~−14.5. Analysis of the total scattering (Bragg plus diffuse components) using reverse Monte Carlo (RMC) modelling indicates that the O²⁻ vacancies preferentially align as pairs in the 〈111〉 cubic directions as the degree of nonstoichiometry increases. This behaviour is discussed with reference to the chemical crystallography of the CeO₂-Ce₂O₃ system at ambient temperature and, in particular, to the nature of the long-range ordering of O²⁻ vacancies within the crystal structure of Ce₇O₁₂.     

网状框架中的机械互锁结构

网状框架具有结晶而延伸的多孔结构,不仅能将多种构筑模块按预期的方式有序组织形成介观材料,也因其可调控的精确结构成为研究基础科学问题的良好平台.机械互锁结构是利用分子间的机械作用将多种分子结合起来以协同实现复杂功能的分子集合体.将网状框架与机械互锁结构结合不仅能实现机械互锁结构的高维度有序组装以协同实现更复杂的分子机器的功能,也有望对更有应用前景的固相中机械互锁结构间的相互作用和微观机理有更深入的认识.本综述介绍了网状框架与机械互锁结构结合的研究领域的重要进展,第一部分在分别简要介绍网状框架和机械互锁结构的基础上阐述了两个领域结合的意义和策略;第二部分主要介绍了机械互锁结构作为构筑模块参与网状框架构建的系统性和代表性工作,包括含轮烷和索烃的构筑模块;第三部分则是介绍由机械互锁作用为主要相互作用构筑的网状框架,包括弹性编织框架和机械互锁框架,最后对全文进行总结并对该领域的后续发展方向予以探讨.     

内电场与光催化性能调控

光生载流子的高效分离是提升光催化反应效率的重要步骤.近年来,内电场作为提高载流子分离效率的内在驱动力而成为光催化材料研究领域的热点之一.本文综述了国内外通过内电场调控光催化性能的研究动态和主要成果.内电场不仅是电子和空穴分离的内在驱动力,而且影响半导体材料费米能级的变化及载流子浓度分布,进而调控了光催化材料导带和价带的弯曲程度及载流子迁移路径.光催化材料内电场的产生机制主要有铁电材料极化、p-n异质结/多晶结、极化表面、晶面间及非线性光学材料内电场等方式,这些方式有效地提高了光生载流子的分离效率,降低电子和空穴复合的几率,从而进一步提高其光催化性能.最后,本文对构建内电场的未来发展趋势进行了展望,并强调了利用先进物理技术并结合理论计算方法来表征内电场的分布及作用的重要性.