Synthesis of todorokite

Todorokite of chemical composition (Mg(0.77)Na(0.03))(Mg(0.18)Mn(2+)(0.60)Mn(4+)(5.22)22) O(12).3.07 H(2)O was synthesized by a two-step procedure. First, sodium birnessite was synthesized and magnesium was exchanged for sodium to form magnesium birnessite, which was autoclaved under a saturated steam pressure at 155 degrees C for 8 hours to form well-crystallized todorokite. Synthesized todorokite particles consisted of fibers extending from a central plate. The plate itself was made of twinned fibers forming a trilling pattern. The infrared spectra and x-ray diffraction patterns were similar to those of natural todorokite samples. Calcium birnessite and nickel birnessite, when autoclaved under conditions similar to those for magnesium birnessite, yielded a todorokite structure. However, the formation of todorokite from calcium and nickel birnessite was less extensive.     

Kinetics of the fe2+-mg, order-disorder reaction in anthophyllites: quantitative cooling rates

The kinetics of the Fe(2+)-Mg, order-disorder phenomenon in a highly ordered natural anthophyllite have been determined over the temperature range from 400 degrees to 720 degrees C at a pressure of 2 kilobars. At temperatures of 600 degrees C and above, equilibrium is attained by disordering as well as ordering reactions. The intracrystalline exchange is defined by a standard Gibbs free energy of 4247 +/- 54 calories per formula unit. Rate studies at 550 degrees and 500 degrees C show that equilibrium is attained by ordering but not by disordering within the same time scale and that the exchange reaction is characterized by an activation energy of approximately 55 kilocalories per formula unit. An equilibration temperature for the natural anthophyllite of 270 degrees C is determined from the termination of the ordering process owing to excessively slow reaction kinetics after approximately 10(7) years. From the rate constants of the exchange process, for different crystallization temperatures, the apparent equilibration temperature of 270 degrees C defines a maximum linear cooling rate for the rock of 1 x 10(4) degrees C per year.     

Crystalline todorokite associated with biogenic debris in manganese nodules

Platy intergrowths of crystalline todorokite are associated with biogenic debris in the cores of manganese nodules from a site in the Pacific Ocean. Analyses by electron diffraction and transmission electron microscopy demonstrate that this material is composed of tunnels of chains of linked MnO(6) octahedra. The chemical composition, morphology, and stability of the todorokite differ from those of nickel-and copper-rich manganese oxides in nodules that have been identified as todorokite or buserite in earlier investigations.     

微波快速合成钙锰矿的影响因素

以通O2氧化Mn(OH)2制备的水钠锰矿为前驱物,采用微波加热合成钙锰矿,并探讨微波的功率、反应温度、时间和pH值等条件对钙锰矿形成的影响。结果表明:一定微波条件下可快速合成粒径均一、结晶度较好的钙锰矿。当微波辐照功率大于150 W时,随着微波功率升高,合成钙锰矿所需时间缩短,600 W功率下20min即可快速得到钙锰矿;温度越高合成钙锰矿所需时间也越短,体系温度为100℃时不能生成钙锰矿,但升高到140℃时,20min即可合成出钙锰矿;在酸性条件下合成钙锰矿的转化率低,而中性和碱性条件下钙锰矿的形成速度快、转化率高、结晶度好。     

圆锥八仙菊花红色素提取及稳定性

以圆锥八仙花(Hydraangea paniculata Sieb.)新鲜粉红花瓣为原材料,通过正交试验确定了圆锥八仙花红色素最佳浸提条件,即:使用pH值为2的60%乙醇溶液,以料液比为1 g:20 mL,在80℃下提取6 h.该红色素在酸性条件下稳定性好,具有较好的耐热性及一定的耐光性,不耐氧化还原剂,Cu2+、Fe...     

水曲柳SRAP分子标记反应系统的优化

以水曲柳叶片DNA为模板,利用SRAP(相关序列多态性)技术及L_(16)(4~5)正交试验和单因子试验方法,分析了不同浓度的DNA模板、Mg~(2+)、dNTP、引物、TaqDNA聚合酶对扩增结果的影响,最终确立的PCR最佳反应系统为:20μL体系中,2×PCR buffer、DNA模板50～100ng,Mg~(2+) 的浓度2.0mmol/L,dNTP0.15mmol/L,引物0.30μmol/L,TaqDNA聚合酶1.0U;最佳退火温度50℃.在此反应系统下,所扩增谱带清晰、稳定、多态性高.     

High-temperature molecular magnets based on cyanovanadate building blocks: spontaneous magnetization at 230 k

The molecular-based magnetic materials Cs(2)Mn(||)[V(||)(CN)(6)] (1) and (Et(4)N)(0.5)Mn(l.25)- [V(CN)(5)].2H(2)O (2) (where Et is ethyl) were prepared by the addition of manganese(II) triflate to aqueous solutions of the hexacyanovanadate(II) ion at 0 degrees C. Whereas 1 crystallizes in a face-centered cubic lattice, 2 crystallizes in a noncubic space group. The cesium salt (1) has features characteristic of a three-dimensional ferrimagnet with a Néel transition at 125 kelvin. The tetraethylammonium salt (2) also behaves as a three-dimensional ferrimagnet with a Néel temperature of 230 kelvin; only two other molecular magnets have higher magnetic ordering temperatures. Saturation magnetization measurements indicate that in both compounds the V(II) and high-spin Mn(II) centers are antiferromagnetically coupled. Both 1 and 2 exhibit hysteresis loops characteristic of soft magnets below their magnetic phase-transition temperatures. The high magnetic ordering temperatures of these cyano-bridged solids confirm that the incorporation of early transition elements into the lattice promotes stronger magnetic coupling by enhancing the backbonding into the cyanide pi* orbitals.     

Carbynes in meteorites: detection, low-temperature origin, and implications for interstellar molecules

Carbon from the Allende meteorite is not graphite but carbyne (triply bonded elemental carbon), inasmuch as on heating to 250 degrees to 330 degrees C it releases mainly triply bonded fragments: -(C identical withC)(n),- with n = 1 to 5, and -(C identical withC)(n)-CN, with n = 1 to 3. Although carbynes have been known to form only by condensation of carbon vapor above 2600 K or by explosive shock of > 600 kilobars, it is found that they also form metastably by the reaction 2CO --> CO(2) + C (solid) at 300 degrees to 400 degrees C in the presence of a chromite catalyst. Such low-temperature formation by surface catalysis may be the dominant source of carbynes on the earth and in meteorites, and a major source of interstellar carbynes and cyanopolyacetylenes.     

Ammonium micas: possible sources of atmospheric ammonia and nitrogen

Ammonium muscovite, NH(4)Al(2)AlSi(3)O(10)(OH)(2), and ammonium phlogopite, NH(4)Mg(3)AlSi(3)O(10)(OH)(2), have been synthesized hydrothermally at gas pressures of 2 kilobars and temperatures between 550 degrees and 730 degrees C. Both micas are stable only in environments of high ammonia fugacity. Ammonia or nitrogen, or both, are released by thermal decomposition, cation exchange, or oxidation. The ammonia : nitrogen ratio in the gas depends primarily on the hydrogen fugacity and the temperature of the environment. Calculations show that, even in a predifferentiated Earth, nitrogen may have predominated. The total amount of nitrogen present on the surface of Earth could be accounted for by the decomposition of a layer of ammonium muscovite 170 meters thick.     

MnO2电极可充性能的研究—化学改性法

本文通过石墨共沉淀这一化学改性法，证实廉价易得的石墨材料对Mno_2电极的可充性有一定的改善。经过化学反应使Mn（OH）_2与石墨共沉淀，通氧气使Mn（OH）_2氧化成Mn_2O_3，干燥脱水后的Mn_2O_3再经酸化歧化成为所需MnO_2样品，并探讨了石墨选型对MnO_2电极改性的影响．     

Microporous and photoluminescent chalcogenide zeolite analogs

Crystalline semiconducting sulfide and selenide zeolite analogs were synthesized that possess four-connected, three-dimensional tetrahedral networks built from tetravalent (M4+ = Ge4+ or Sn4+, where M = meta) and trivalent (M3+ = Ga3+ or In3+) cations. Microporous materials were obtained in all four combinations of M4+ and M3+, and some of them were thermally stable up to at least 380 degrees C. These materials exhibit framework topologies with pore size ranging from 12 to 24 tetrahedral atoms, high surface area, high framework charge density and ion exchange capacity, and tunable electronic and optical properties.     

Evidence of thermal metamorphism on the C, g, B, and f asteroids

Reflectance spectra (0.3 to 2.6 micrometers) of 14 C, G, B, and F asteroids and 21 carbonaceous chondrite powders are compared in detail. Only three thermally metamorphosed CM-Cl chondrites that have a weak ultraviolet absorption are shown to have close counterparts among those asteroids. Reflectance spectra of heated Murchison CM2 chondrite are compared with the average C and G type asteroid spectra. Murchison heated at 600 degrees to 1000 degrees C exhibits a similar weak ultraviolet absorption and provides the best analog for those spectra. Comparison of ultraviolet absorption strengths between 160 C, G, B, and F asteroids and carbonaceous chondrites suggests that surface minerals of most of those asteroids are thermally metamorphosed at temperatures around 600 degrees to 1000 degrees C.     

Open Framework Structures Based on Sex2- Fragments: Synthesis of (Ph4P)[M(Se6)2] (M = Ga, In, TI) in Molten (Ph4P)2Sex

Polychalcogenide compounds with open polymeric frameworks are rare, and they represent a class of compounds in which microporosity might be achieved. Microporous frameworks that are not oxide-based are now attracting interest because of the combination of catalytic and electronic properties they may simultaneously possess. Three new compounds that may be forerunners to such materials have been discovered and are reported here. The reaction of gallium (Ga), indium (In), and thallium (TI) metal with (Ph(4)P)(2)Se(5) (Ph, phenyl) and an excess of elemental selenium (Se) in a sealed, evacuated Pyrex tube at 200 degrees C yielded small red crystals of (Ph(4)P)[Ga(Se(6))(2)] (I), (Ph(4)P)[In(Se(6))(2)] (II), and (Ph(4)P)[TI(Se(6))(2)] (III), respectively. The [M(Se(6))(2)](-) (M = Ga, In, TI) ions form a two-dimensional, open framework filled with Ph(4)P(+) ions. The [M(Se(6))(2)](n)(n-) structure consists of tetrahedral M(3+) centers and bridging Se(6)(2-) ligands, leading to an extended structure in two dimensions. These layers stack perfectly one on top of the other giving rise to one-dimensional channels running down the c axis that are filled with Ph(4)P(+) cations. These cations are situated in the layers, as opposed to between the layers, and the whole structure can be viewed as a template. Compound II shows remarkable thermal stability and melts congruently at 242 degrees C. Upon cooling to room temperature it gives a glassy phase that recrystallizes upon subsequent heating to 160 degrees C.     

Kinetic evidence for five-coordination in AlOH(aq)2+ ion

Trivalent aluminum ions are important in natural bodies of water, but the structure of their coordination shell is a complex unsolved problem. In strong acid (pH < 3.0), Al(III) exists almost entirely as the octahedral Al(H2O)6(3+) ion, whereas in basic conditions (pH > 7), a tetrahedral Al(OH)(4- structure prevails. In the biochemically and geochemically critical pH range of 4.3 to 7.0, the ion structures are less clear. Other hydrolytic species, such as AlOH(aq)2+, exist and are traditionally assumed to be hexacoordinate. We show, however, that the kinetics of proton and water exchange on aqueous Al(III), coupled with Car-Parrinello simulations, support a five-coordinate Al(H2O)4OH2+ ion as the predominant form of AlOH(aq)2+ under ambient conditions. This result contrasts Al(III) with other trivalent metal aqua ions, for which there is no evidence for stable pentacoordinate hydrolysis products.     

有机,无机改良剂对酸性硫酸盐土化学动力学与水稻生长的影响

研究了稻秆、碳酸钙和二氧化锰改良剂对淹水的酸性硫酸盐土的电化学、化学动力学、水稻生长及产量的影响. 施用稻秆(干土重的0.25％)显著影响土壤的还原作用.高浓度的亚铁使水稻前期生长受阻;但亚铁的浓度随后逐渐降低,水稻生长繁茂,谷粒和茎秆产量反较高,植株的含钾量也增高. 加入酸酸钙(相当于干土重的0.25％)明显提高了土壤的pH值,降低土壤的Eh和EC值,并显著降低了水溶性亚铁、亚锰和铝的浓度.碳酸钙或碳酸钙加二氧化锰的处理,都能降低土壤溶液中亚铁的浓度,显著增加稻谷和稻杆的产量,此外,这两种处理都会降低生长前期植株中锌的含量. 加入二氧化锰(干土重的0.005％),使土壤溶液中的亚锰量增多,植株的铁锰比率降低,水稻产量比对照显著增加. 研究结果表明,稻杆是一种改良酸性硫酸盐土较经济的改良剂,其价值值得进一步研究.     

Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores

Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms. The SBA-15 materials are synthesized in acidic media to produce highly ordered, two-dimensional hexagonal (space group p6mm) silica-block copolymer mesophases. Calcination at 500 degrees C gives porous structures with unusually large interlattice d spacings of 74.5 to 320 angstroms between the (100) planes, pore sizes from 46 to 300 angstroms, pore volume fractions up to 0.85, and silica wall thicknesses of 31 to 64 angstroms. SBA-15 can be readily prepared over a wide range of uniform pore sizes and pore wall thicknesses at low temperature (35 degrees to 80 degrees C), using a variety of poly(alkylene oxide) triblock copolymers and by the addition of cosolvent organic molecules. The block copolymer species can be recovered for reuse by solvent extraction with ethanol or removed by heating at 140 degrees C for 3 hours, in both cases, yielding a product that is thermally stable in boiling water.     

Kyanite-Andalusite Equilibrium from 700{degrees} to 800{degrees}C

The metastable kyaniteandalusite equilibrium in the Al(2)SiO(5) system has been reversed at 700 degrees , 750 degrees , and 800 degrees C at elevated water pressures, with a variety of natural and synthetic kyanites and andalusites as starting materials. Sillimanite, the stable form of Al(2)SiO(5) under these conditions, did not appear. The value of the transition pressure at 750 degrees C is 6.6 +/- 0.4 kilobars, several kilobars below pressures given by several convergent previous determinations. The Al(2)SiO(5) pressure-temperature triple point now indicated lies far from the points found by others. The revised aluminum silicate phase diagram indicates that many rocks crystallized at lower pressures than formerly thought possible.     

Ordering of V2+, Mn2+, and Fe3+ Ions in Zoisite, Ca2Al3Si3O12(OH)

The presence of very small amounts of Mn(2+), V(2+), and Fe(3+) ions in zoisite can be easily detected by the electron paramagnetic resonance technique at room temperature. The Mn(2+) and Fe(3+) ions are completely ordered and are probably located in the Ca(1)- and Al(II)-sites, respectively, whereas the V(2+) ions probably occupy both Ca(1)- and Ca(2)-sites, with a preference for the Ca(1)-site.     

Ionic radon solutions

Radon is oxidized between -195 degrees and 25 degrees C by chlorine fluorides, bromine fluorides, iodine heptafluoride, and NiF(6)(2)- ion in hydrogen fluoride with the formation of stable solutions of radon fluoride. Electromigration studies show that the radon is present as a cation, possibly Rn(2)+ or RnF+, in several conducting solutions.     

Age and Duration of Weathering by 40K-40Ar and 40Ar/39Ar Analysis of Potassium-Manganese Oxides

Supergene cryptomelane [K(1-2)(Mn(3+)Mn(4+))(8)O(16). chiH(2)O] samples from deeply weathered pegmatites in southeastern Brazil subjected to (40)K-(40)Ar and (40)Ar/(39)Ar analysis yielded (40)K-(40)Ar dates ranging from 10.1 +/- 0.5 to 5.6 +/- 0.2 Ma (million years ago). Laser-probe (40)Ar/(39)Ar step-heating of the two most disparate samples yielded plateau dates of 9.94 +/- 0.05 and 5.59 +/- 0.10 Ma, corresponding, within 2 sigma, to the (40)K-(40)Ar dates. The results imply that deep weathering profiles along the eastern Brazilian margin do not reflect present climatic conditions but are the result of a long-term process that was already advanced by the late Miocene. Weathering ages predate pulses of continental sedimentation along the eastern Brazilian margin and suggest that there was a time lag between weathering and erosion processes and sedimentation processes.