Pressure-induced amorphization and negative thermal expansion in ZrW2O8

It has recently been shown that zirconium tungstate (ZrW2O8) exhibits isotropic negative thermal expansion over its entire temperature range of stability. This rather unusual behavior makes this compound particularly suitable for testing model predictions of a connection between negative thermal expansion and pressure-induced amorphization. High-pressure x-ray diffraction and Raman scattering experiments showed that ZrW2O8 becomes progressively amorphous from 1.5 to 3.5 gigapascals. The amorphous phase was retained after pressure release, but the original crystalline phase returned after annealing at 923 kelvin. The results indicate a general trend between negative thermal expansion and pressure-induced amorphization in highly flexible framework structures.     

Hydrogen clusters in clathrate hydrate

High-pressure Raman, infrared, x-ray, and neutron studies show that H2 and H2O mixtures crystallize into the sII clathrate structure with an approximate H2/H2O molar ratio of 1:2. The clathrate cages are multiply occupied, with a cluster of two H2 molecules in the small cage and four in the large cage. Substantial softening and splitting of hydrogen vibrons indicate increased intermolecular interactions. The quenched clathrate is stable up to 145 kelvin at ambient pressure. Retention of hydrogen at such high temperatures could help its condensation in planetary nebulae and may play a key role in the evolution of icy bodies.     

In situ observations of a high-pressure phase of H2O Ice

A previously unknown solid phase of H2O has been identified by its peculiar growth patterns, distinct pressure-temperature melting relations, and vibrational Raman spectra. Morphologies of ice crystals and their pressure-temperature melting relations were directly observed in a hydrothermal diamond-anvil cell for H2O bulk densities between 1203 and 1257 kilograms per cubic meter at temperatures between -10 degrees and 50 degreesC. Under these conditions, four different ice forms were observed to melt: two stable phases, ice V and ice VI, and two metastable phases, ice IV and the new ice phase. The Raman spectra and crystal morphology are consistent with a disordered anisotropic structure with some similarities to ice VI.     

A-Axis--Oriented YBa2Cu3O7/PrBa2Cu3O7 Superlattices

A modulated structure has been fabricated from high transition temperature superconductors where the individual CuO(2) planes are composed of alternating superconducting and insulating strips. This structure is made by growing a-axis-oriented YBa(2)Cu(3)O(7)/PrBa(2)Cu(3)O(7) superlattices by 90 degrees off-axis sputtering on (100)SrTiO(3) and (100)LaAlO(3) substrates. Superlattice modulation is observed to a modulation wavelength of 24 angstroms (12 angstroms-YBa(2)Cu(3)O(7)/12 angstroms-PrBa(2)Cu(3)O(7)), both by x-ray diffraction and by cross-sectional transmission electron microscopy. Rutherford backscattering spectroscopy indicates a high degree of crystalline perfection with a channeling minimum yield of 3 percent. Quasi-one-dimensional conductivity should be obtainable in these structures.     

Visual Observations of the Amorphous-Amorphous Transition in H2O Under Pressure

The vapor-deposited low-density amorphous phase of H(2)O was directly compressed at 77 kelvin with a diamond-anvil cell, and the boundary between the low-density amorphous phase and the high-density amorphous phase was observed while the sample was warmed under compression. The transition from the low-density amorphous phase to the high-density amorphous phase was distinct and reversible in an apparently narrow pressure range at approximately 130 to approximately 150 kelvin, which provided experimental evidence for polymorphism in amorphous H(2)O.     

超声/紫外/O3/H2O2处理去除水中DDT的研究

[目的]研究超声/紫外/O3/H2O2处理去除水中DDT的效果,为建立新的去除水中DDTs的AOPs技术提供参考。[方法]配制一定浓度的DDT水溶液,分别采用超声、紫外、O3/H2O2、超声/紫外和超声/紫外/O3/H2O2组合处理,并用超声/紫外/O3/H2O2组合处理北江佛山段水样,用GC-EDC方法检测DDT含量变化,比较各处理方法的DDT去除率。[结果]水中DDT去除率分别为:超声波处理为45%～56%、紫外光处理近70%、超声/紫外联合处理超过80%、O3/H2 O2处理为28%～32%、超声/紫外/O3/H2 O2处理为91%,而北江水样DDT去除率达到85%。[结论]超声/紫外/O3/H2O2联合处理可有效去除水中DDT。     

O3与O3/H2O2两个体系降解除草剂2,4-D反应特性研究

分别采用O3、O3/H2O2体系降解苯氧羧酸类除草剂2,4-D,探讨了降解过程中反应温度、pH值、O3混合气流量、有机物初始浓度等操作条件的变化对降解动力学的影响。结果发现,温度和pH值的影响较大,O3流量影响最小,温度升高、pH值增大、臭氧流量增加、2,4-D初始浓度降低均有助于降解速率的提高。O3/H2O2体系中,H2O2能促进O3分解产生大量自由基,导致2,4-D反应活化能降低。和O3相比,O3/H2O2体系降解效果好,降解时间短,反应条件温和,操作费用低,是很有发展前景的高级氧化技术。     

A functional model for O-O bond formation by the O2-evolving complex in photosystem II

The formation of molecular oxygen from water in photosynthesis is catalyzed by photosystem II at an active site containing four manganese ions that are arranged in di-mu-oxo dimanganese units (where mu is a bridging mode). The complex [H2O(terpy)Mn(O)2Mn(terpy)OH2](NO3)3 (terpy is 2,2':6', 2"-terpyridine), which was synthesized and structurally characterized, contains a di-mu-oxo manganese dimer and catalyzes the conversion of sodium hypochlorite to molecular oxygen. Oxygen-18 isotope labeling showed that water is the source of the oxygen atoms in the molecular oxygen evolved, and so this system is a functional model for photosynthetic water oxidation.     

PbO-Bi2O3-B2O3系统玻璃中B3+离子的配位状态

利用红外光谱和喇曼光谱研究了ＰｂＯ－Ｂｉ２Ｏ３－Ｂ２Ｏ３系统玻璃结构中Ｂ＾３＋离子的配位状态，研究结果表明：当Ｂ２Ｏ３含量较低时，获得的重金属氧化物玻璃结构中的Ｂ＾３＋离子以单个［ＢＯ３］三角体形式存在，随Ｂ２Ｏ３含量增加，部分［ＢＯ３］三角体转变成［ＢＯ３］三角体转变成［ＢＯ４］四面体；当Ｂ２Ｏ３含量增加到一定程度时，通过［ＢＯ３］三角体与［ＢＯ４］四面体之间的桥氧离子的联接而形成含［ＢＯ３］三     

烟草叶片发育过程中抗坏血酸-谷胱甘肽循环清除H2 O2 的研究

[目的]研究烟草叶片发育过程中H2O2积累以及抗坏血酸-谷胱甘肽(AsA-GSH)循环清除H2O2能力的变化。[方法]以烟草(Nicotiana tabacumL.cvNC89&JYH)为材料,研究了叶片发育过程中H2O2积累与AsA-GSH循环的关联。[结果]结果表明,抗坏血酸过氧化物酶(APX)、谷胱甘肽还原酶(GR)活性,AsA、GSH含量在叶片幼嫩及成熟时期维持较高水平,衰老时下降较快,与H2O2含量存在相关性,且AsA-GSH循环系统在运行过程中保持平衡。[结论]AsA-GSH循环系统的运行与H2O2代谢存在相关性。     

H2O2对陈化马铃薯切片抗氰呼吸的诱导作用研究

研究了H₂O₂对陈化马铃薯切片抗氰呼吸的诱导作用.用切片和纯化线粒体进行测定的结果均表明外源H₂O₂(5.0 mmol/L)处理对陈化马铃薯切片的总呼吸只有微弱的影响,但却可以明显诱导切片的抗氰呼吸,并显著提高抗氰呼吸对总呼吸的贡献.应用交替氧化酶的单克隆抗体进行Western杂交的结果表明,H₂O₂处理可以增强陈化马铃薯切片中交替氧化酶的表达,表明H₂O₂对抗氰呼吸的诱导作用与其时交替氧化酶表达的诱导有关.抗氰呼吸可能参与了H₂O₂调控植物抗病防御反应的作用机制.     

外源H2O2对拟南芥气孔运动的影响

[目的]探究外源过氧化氢(H2O2)对气孔运动的影响。[方法]利用外源H2O2诱导、药理学和气孔分析方法证明H2O2参与调节气孔运动。[结果]在一定范围内,随H2O2浓度的增加,对气孔关闭的促进效果逐渐增大,其最适浓度为100μmol/L,但该效应可被抗坏血酸(Vc)和过氧化氢酶(CAT)所逆转。[结论]H2O2能促进气孔关闭,作为信号分子参与气孔运动的调节。     

A New High-Temperature Superconductor: Bi2Sr3-x Cax Cu2O8+y

A new superconductor that displays onset behavior near 120 K has been identified as Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y), with x ranging from about 0.4 to 0.9. Single crystal x-ray diffraction data were used to determine a pseudo-tetragonal structure based on an A-centered orthorhombic subcell with a = 5.399 A, b= 5.414A, and c = 30.904 A. The structure contains copper-oxygen sheets as in La(2)CuO(4) and YBa(2)Cu(3)O(7), but the copper-oxygen chains present in YBa(2)Cu(3)O(7) do not occur in Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y). The structure is made up of alternating double copper-oxygen sheets and double bismuth-oxygen sheets. There are Ca(2+) and Sr(2+) cations between the adjacent Cu-O sheets; Sr(2+) cations are also found between the Cu-O and Bi-O sheets. Electron microscopy studies show an incommensurate superstructure along the a axis that can be approximated by an increase of a factor of 5 over the subcell dimension. This superstructure is also observed by x-ray diffraction on single crystals, but twinning can make it appear that the superstructure is along both a and b axes. Flux exclusion begins in our samples at about 116 K and is very strong by 95 K. Electrical measurements on a single crystal of Bi(2)Sr(3-x)Ca(x)Cu(2)O(8+y) show a resistivity drop at about 116 K and apparent zero resistivity at 91 K.     

钯修饰电极的制备及其对H_2O_2的电催化还原作用研究

[目的]研究钯化学修饰电极在H2O2检测中的应用。[方法]采用循环伏安法制备了钯修饰的复合陶瓷碳电极(Pd/CCE),研究了该修饰电极对H2O2的电催化性能。[结果]在含有PdCl2.2H2O的H2SO4溶液中(pH 1.2),控制扫描电位范围为0～1.0 V(vs.SCE)连续扫描40圈时制得的Pd/CCE修饰电极对H2O2具有较强的电催化活性,安培法检测H2O2的线性范围为6.0×10-5～1.0×10-2mol/L,检出限为2.2×10-5mol/L(3Sb)。[结论]直接电沉积得到的钯修饰电极,可实现较低电位下测定H2O2,且电极具有制作简单、价格低廉、响应时间短和表面容易更新等特点。     

外源多胺促进的霍山石斛类原球茎芽发生与H2O2代谢的关系

[目的]研究外源多胺促进霍山石斛类原球茎芽的发生与过氧化氢(H_2O_2)代谢酶活性的关系。[方法]主要测定了外源多胺处理后H_2O_2的动态变化和代谢酶的活性。[结果]外源多胺在有效促进芽发生的同时也能显著提高培养物中H_2O_2的含量,2.0 mmol/L亚精胺(Spd)或腐胺(Put)处理5 d的培养物中H_2O_2含量分别比对照组高175.6%和180.6%,添加H_2O_2淬灭剂二甲基硫脲(DMTU)可抑制类原球茎芽的发生,补充Spd或Put可部分解除DMTU的抑制作用。在外源多胺处理前期和中期,虽然超氧化物歧化酶(SOD)和过氧化物酶(POD)活性无明显改变,但合成H_2O_2的多胺氧化酶(PAO)活性和分解H_2O_2的抗坏血酸过氧化物酶(APX)与过氧化氢酶(CAT)活性明显增加。[结论]外源多胺作用的霍山石斛类原球茎芽的发生与H_2O_2积累和分解代谢有关。     

超声辅助磁性纳米四氧化三铁催化过氧化氢降解亚甲蓝染料的研

建立了一种基于超声辅助磁性四氧化三铁纳米微粒催化过氧化氢降解亚甲蓝染料的方法,研究了四氧化三铁纳米微粒浓度、过氧化氢浓度、pH值、反应时间、超声时间和温度等对催化降解反应的影响.结果表明,当四氧化三铁纳米粒子浓度为600mg/L,过氧化氢浓度为0.32mol/L,pH值为5,超声时间为3min,温度为30℃,反应时间为2h时,模拟染料废水中亚甲蓝的去除率最高可达到95%.     

Size-Specific Infrared Spectra of Benzene-(H2O)n Clusters (n = 1 through 7): Evidence for Noncyclic (H2O)n Structures

Resonant ion-dip infrared spectroscopy has been used to record size-specific infrared spectra of C(6)H(6)-(H(2)O)n clusters with n = 1 through 7 in the O-H stretch region. The O-H stretch spectra show a dramatic dependence on cluster size. For the n = 3 to 5 clusters, the transitions can be divided into three types-attributable to free, pi hydrogen-bonded, and single donor water-water O-H stretches-consistent with a C(6)H(6)-(H(2)O)n structure in which benzene is on the surface of a cyclic (H(2)O)n cluster. In n = 6 and 7 clusters, the spectra show distinct new transitions in the 3500 to 3600 wave number region. After comparison of these results with the predictions of ab initio calculations on (H(2)O)n clusters, these new transitions have been assigned to double donor O-H stretches associated with the formation of a more compact, noncyclic structure beginning with (H(2)O)(6). This is the same size cluster for which ab initio calculations predict that a changeover to noncyclic (H(2)O)n structures will occur.     

Interhemispheric Differences in Polar Stratospheric HNO3, H2O, CIO, and O3

Simultaneous global measurements of nitric acid (HNO(3)), water (H(2)O), chlorine monoxide (CIO), and ozone (O(3)) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO(3) was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H(2)O after mid-July. By mid-August, near the time of peak CIO, abundances of gas-phase HNO(3) and H(2)O were extremely low. The concentrations of HNO(3) and H(2)O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO(3) or H(2)O were observed in the 1992-1993 Arctic winter vortex. Although CIO was enhanced over the Arctic as it was over the Antarctic, Arctic O(3) depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone "hole" is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.     

Moissanite: a window for high-pressure experiments

We achieved a pressure of 52.1 gigapascals with moissanite anvils, which have optical, thermal, electric, magnetic, and x-ray properties that rival those of diamond. The mode-softening of D(2)O toward the pressure-induced hydrogen bond symmetrization and the Raman shifts of diamond under hydrostatic and nonhydrostatic compressions were studied with moissanite anvils in the spectral regions normally obscured by diamond anvils. Moissanite anvil cells allow maximum sample volumes 1000 times larger than those allowed by diamond anvil cells and may enable the next level of advancement in high-pressure experiments.     

Hydrocalcite (CaCO3 * H2O) and Nesquehonite (MgCO3 * 3H2O) in Carbonate Scales

Hydrocalcite (CaCO(3) * H(2)O) with exactly one molecule of hydrate water is the main component of carbonate scales deposited from cold water in contact with air. When the magnesium content of the water is high, the hydrocalcite occurs together with MgCO(3) * 3H(2)O (nesquehonite). From the conditions under which hydrocalcite is transformed into calcite and aragonite, it appears that in some cases aragonite in nature may be formed by way of an intermediary of CaCO(3) * H(2)O.