Oxygen-Carrying Properties of a Simple Synthetic System

An iridium compound, chloro-carbonyl-bis(triphenylphosphine)-iridium, in solution, takes up molecular oxygen-one molecule per metal atom-which is subsequently recovered by reducing the pressure. The adduct is photosensitive but otherwise stable at ambient temperatures. It is a monomeric molecular complex and probably contains a peroxo group with both oxygens bonded to the same metal atom.     

Major and trace elements and cosmic-ray produced radioisotopes in lunar samples

Analytical data for 42 major and trace elements were mostly obtained by a combination of instrumental and radiochemical neutron activation analyses using both thermal and 14-million-electronvolt neutrons. Excesses of nitrogen and chlorine in the fines, compared with the rocks, are attributed to the solar wind. A striking similarity for contents of seven elements in lunar metal and metal from the calcium-rich achondrite Juvinas was noted. Fractional dissolution was used to separate five radionuclides produced by cosmic-ray bombardment in the fines and rock 57-40. Results for argon-39 from the reaction potassium-39 (n,p), and for argon-37, from the reaction calcium-40 (n,a), seem to require a neutron spectrum conitaining more neutrons below 2 million electronvolts than the evaporation spectrum or that given by Arnold, Honda, and Lal (1) or a strong time dependence for the neutron flux.     

Detection of smoking-related covalent DNA adducts in human placenta

The presence of covalent DNA chemical addition products (adducts) in human term placentas was investigated by recently developed immunologic and 32P-postlabeling assays. DNA from placental specimens of smokers showed a small but not statistically significant increase in adduct levels when tested by antibodies to DNA modified with a benzo[a]pyrene dihydrodiol epoxide (BPDE-I), the ultimate carcinogenic derivative of benzo[a]pyrene. The postlabeling assay detected several modified nucleotides, one of which (adduct 1) strongly related to maternal smoking during pregnancy. This adduct was present in placental tissue from 16 of 17 smokers, but only 3 of 14 nonsmokers. Among smokers, levels of adduct 1 in general were only weakly related to questionnaire and biochemical measures of the intensity of smoking exposures, which suggests modulation by individual susceptibility factors. The adduct seemed to be derived from an aromatic carcinogen, but it may not result from several of the most intensely studied polycyclic aromatic hydrocarbons or aromatic amines in tobacco smoke. The data show the association of cigarette smoking with covalent damage to human DNA in vivo.     

Crystal and molecular structure of a thymine-thymine adduct

Thymine-thymine adduct is a product isolated from thymine irradiated with ultraviolet light in frozen aqueous solution. This compound is presumably formed through the rearrangement of an initial photoproduct. Single crystal x-ray diffraction analysis has confirmed the molecular formula of the adduct, 5-hydroxy-6-4'-(5'-methylpyrimid-2'-one)-dihydrothymine, except for the possibility of a hydrogen atom on the 3' nitrogren rather than the 1' nitrogen, and has established the stereoconfiguration of the molecule.     

Probing the structure of metal cluster-adsorbate systems with high-resolution infrared spectroscopy

High-resolution infrared laser spectroscopy was used to obtain rotationally resolved infrared spectra of adsorbate-metal complexes. The method involves forming the bare metal clusters in helium nanodroplets and then adding a molecular adsorbate (HCN) and recording the infrared spectrum associated with the C-H stretching vibration. Rotationally resolved spectra were obtained for HCN-Mg(n) (n = 1 to 4). The results suggest a qualitative change in the adsorbate-metal cluster bonding with cluster size.     

Mechanism of the rhodium porphyrin-catalyzed cyclopropanation of alkenes

The rhodium porphyrin-catalyzed cyclopropanation of alkenes by ethyl diazoacetate (EDA) is representative of a number of metal-mediated cyclopropanation reactions used widely in organic synthesis. The active intermediate in these reactions is thought to be a metal carbene complex, but evidence for the involvement of metal-olefin pi complexes has also been presented. Low-temperature infrared and nuclear magnetic resonance spectroscopies have been used to characterize a rhodium porphyrin-diazoalkyl adduct that results from the stoichiometric condensation of the catalyst and EDA. Optical spectroscopy suggests that this complex is the dominant steady-state species in the catalytic reaction. This compound decomposes thermally to provide cyclopropanes in the presence of styrene, suggesting that the carbene is indeed the active intermediate. Metal-alkene pi complexes have also been detected spectroscopically. Kinetic studies suggest that they mediate the rate of carbene formation from the diazoalkyl complex but are not attacked directly by EDA.     

Mossbauer Spectrum of Iron-57 in Iron Metal at Very High Pressures

The effect of pressure on the M?ssbauer spectrum of Fe(57) in iron metal has been studied as the pressure was increased presumably to more than 140 kbar. At pressures up to 120 kbar, a six-line spectrum characteristic of alpha-iron was observed. At 140 kbar, a seventh line appeared in the spectrum at -0.12 +/- 0.06 mm/sec relative to stainless steel. This line was attributed to the appearance of the high-pressure phase of iron.     

Fractionation of the platinum-group elements during mantle melting

Experiments in sulfide-silicate systems demonstrate that two sulfide phases are stable in the asthenospheric upper mantle: a crystalline osmium-iridium-ruthenium-enriched monosulfide and a rhodium-platinum-palladium-enriched sulfide melt. During silicate melt segregation, monosulfide stays in the solid residue, dominating the noble metal spectrum of residual mantle. The sulfide melt is entrained as immiscible droplets in the segregating silicate melt, defining the noble metal inventory of the basaltic component.     

Laser-induced fluorescence and bonding of metal dimers

This article describes a technique for the spectroscopic of metal clusters and intermetallic compounds. First, metallic samples are vaporized by a pulsed YAG (yttrium-aluminum garnet) laser, and then the gaseous products are excited with a pulsed-dye laser until they fluoresce. A time-resolved, fluorescence spectrum is then measured by the product. The application of this technique to the study of metal dimers is reviewed, with emphasis on recent results from Be(2) and Cr(2). Studies of such species often yield insights into the chemistry of metals and metal-metal bonding.     

Visualization of the molecular Jahn-Teller effect in an insulating K4C60 monolayer

We present a low-temperature scanning tunneling microscopy (STM) study of K(x)C60 monolayers on Au(111) for 3 < or = x < or = 4. The STM spectrum evolves from one that is characteristic of a metal at x = 3 to one that is characteristic of an insulator at x = 4. This electronic transition is accompanied by a dramatic structural rearrangement of the C60 molecules. The Jahn-Teller effect, a charge-induced mechanical deformation of molecular structure, is directly visualized in the K4C60 monolayer at the single-molecule level. These results, along with theoretical analyses, provide strong evidence that the transition from metal to insulator in K(x)C60 monolayers is caused by the Jahn-Teller effect.     

铽掺杂碳点的制备及其抑菌性能

以马铃薯为原料,通过一步水热法合成碳点,利用稀有金属铽对碳点进行表面修饰,制备铽掺杂碳点(Tb-CDs),通过透射扫描电镜、紫外光谱、红外光谱、荧光光谱等对Tb-CDs进行表征,并研究Tb-CDs在光催化条件下对大肠埃希菌的抑菌作用和对大肠埃希菌做荧光标记的可行性。结果显示,Tb-CDs颗粒小,粒径均匀,分散性好,荧光性强,因其表面富含羧基和羟基等,具有较好的水溶性。在光催化条件下,Tb-CDs对大肠埃希菌具有较好的抑菌作用。当Tb-CDs的质量浓度为0.6 mg·mL^-1,可见光照射60 min时,其对大肠埃希菌的抑菌率可达100%。此外,Tb-CDs能有效地对大肠埃希菌进行荧光标记。     

等离子体发射光谱法测定蕨麻中人体必需金属元素含量的研究

[目的]为了测定蕨麻中人体必需金属元素的含量,从而为开发蕨麻保健品与饮料提供参考。[方法]采用等离子体发射光谱法测定蕨麻中人体必需金属元素(Ca、Cu、Fe、K、Mg、Mn、Na、Zn)含量。[结果]结果表明,等离子体发射光谱法可同时测定蕨麻中的Ca、Cu、Fe、K、Mg、Mn、Na、Zn等多种金属元素。[结论]该研究为藏药蕨麻的进一步研究开发提供了科学依据。     

Viking magnetic properties investigation: further results

The amounts of magnetic particles held on the reference test chart and backhoe magnets on lander 2 and lander 1 are comparable, indicating the presence of an estimated 3 to 7 percent by weight of relatively pure, strongly magnetic particles in the soil at the lander 2 sampling site. Preliminary spectrophotometric analysis of the material held on the backhoe magnets on lander 1 indicates that its reflectance characteristics are indistinguishable from material within a sampling trench with which it has been compared. The material on the RTC magnet shows a different spectrum, but it is suspected that the difference is the result of a reflectance contribution from the magnesium metal covering on the magnet. It is argued that the results indicate the presence, now or originally, of magnetite, which may be titaniferous.     

Efficient photochemical water splitting by a chemically modified n-TiO2

Although n-type titanium dioxide (TiO2) is a promising substrate for photogeneration of hydrogen from water, most attempts at doping this material so that it absorbs light in the visible region of the solar spectrum have met with limited success. We synthesized a chemically modified n-type TiO2 by controlled combustion of Ti metal in a natural gas flame. This material, in which carbon substitutes for some of the lattice oxygen atoms, absorbs light at wavelengths below 535 nanometers and has a lower band-gap energy than rutile (2.32 versus 3.00 electron volts). At an applied potential of 0.3 volt, chemically modified n-type TiO2 performs water splitting with a total conversion efficiency of 11% and a maximum photoconversion efficiency of 8.35% when illuminated at 40 milliwatts per square centimeter. The latter value compares favorably with a maximum photoconversion efficiency of 1% for n-type TiO2 biased at 0.6 volt.     

Multiple energy scales at a quantum critical point

We report thermodynamic measurements in a magnetic-field-driven quantum critical point of a heavy fermion metal, YbRh2Si2. The data provide evidence for an energy scale in the equilibrium excitation spectrum that is in addition to the one expected from the slow fluctuations of the order parameter. Both energy scales approach zero as the quantum critical point is reached, thereby providing evidence for a new class of quantum criticality.     

氧化锌-贵金属异质结构光催化剂的合成进展

单一组分的氧化锌(ZnO)半导体催化剂在光催化过程中存在的光生电荷-空穴易复合以及对光的低利用率等问题限制了其实际应用。最近,新兴的贵金属复合的ZnO基异质结构纳米材料能克服以上单一组分ZnO催化剂的不足而得到了科学家广泛的关注。主要对ZnO-贵金属异质结构光催化剂的合成进展进行简要综述,阐述其催化作用机理,并对其发展前景进行展望。     

Interception of excited vibrational quantum states by O2 in atmospheric association reactions

Bimolecular reactions in Earth's atmosphere are generally assumed to proceed between reactants whose internal quantum states are fully thermally relaxed. Here, we highlight a dramatic role for vibrationally excited bimolecular reactants in the oxidation of acetylene. The reaction proceeds by preliminary adduct formation between the alkyne and OH radical, with subsequent O(2) addition. Using a detailed theoretical model, we show that the product-branching ratio is determined by the excited vibrational quantum-state distribution of the adduct at the moment it reacts with O(2). Experimentally, we found that under the simulated atmospheric conditions O(2) intercepts ~25% of the excited adducts before their vibrational quantum states have fully relaxed. Analogous interception of excited-state radicals by O(2) is likely common to a range of atmospheric reactions that proceed through peroxy complexes.     

Effect of heavy metal salts on the activity and multiple forms of RNases of soybean seedlings after inoculation with Bradyrhizobium japonicum and Sinorhizobium fredii

The investigation of the effect of heavy metal salts on the activity of RNases of soybean seedlings inoculated with soybean rhizobia strains showed changes in specific activity and the spectrum of the multiple forms of the enzyme depending on the concentrations of salts and soybean rhizobia strains.     

X-ray structure of the major adduct of the anticancer drug cisplatin with DNA: cis-[Pt(NH3)2(d(pGpG))

Crystals of the adduct of the anticancer drug cis-diamminedichloroplatinum(II), cis-DDP, with d(pGpG), its putative target on DNA in the cancer cell, have been obtained and used in an x-ray crystallographic study to elucidate the molecular structure to atomic resolution. Each of the four crystallographically independent cis-[Pt(NH3)2(d(pGpG))] molecules is comprised of a square-planar platinum atom bonded to two ammonia ligands and two N(7) atoms of guanosine nucleosides from the same chain. Base stacking of the two adjacent guanine rings is completely disrupted by coordination to the cis-(Pt(NH3)2)2+ unit. Comparison of the backbone and deoxyribose ring torsion angles with those found by previous (nuclear magnetic resonance spectroscopy) studies of this adduct in solution demonstrates that the solid state geometry is substantially the same as that in solution. The relevance of these results to the molecular mechanism of action of cis-DDP is discussed.