Xenon hexafluoride: structural crystallography of tetrameric phases

Three crystalline phases of xenon hexafluoride are based on tetrameric association of XeF(5)(+) and F(-) ions into eight-membered rings. Phase I (monoclinic, 8 XeF(6) units per cell) transforms at approximately 10 degrees C to phase II (orthorhombic, 16 XeF(6) units per cell), which in turn transforms at approximately -25 degrees C to phase 111 (monoclinic, 64 XeF(6) units per doubly primitive cell). The transformation from phase I to phase II requires gross reorientation of half of the tetramers in the structure. The transformation from phase II to phase III involves only an ordering of right-handed and left-handed configurations.     

An ultradense polymorph of rutile with seven-coordinated titanium from the Ries crater

We report the discovery of an ultradense post-rutile polymorph of titanium dioxide in shocked gneisses of the Ries crater in Germany. The microscopic diagnostic feature is intense blue internal reflections in crossed polarizers in reflected light. X-ray diffraction studies revealed a monoclinic lattice, isostructural with the baddeleyite ZrO2 polymorph, and the titanium cation is coordinated with seven oxygen anions. The cell parameters are as follows: a = 4.606(2) angstroms, b = 4.986(3) angstroms, c = 4.933(3) angstroms, beta (angle between c and a axes) = 99.17(6) degrees; space group P2(1)/c; density = 4.72 grams per cubic centimeter, where the numbers in parentheses are standard deviations in the last significant digits. This phase is 11% denser than rutile. The mineral is sensitive to x-ray irradiation and tends to invert to rutile. The presence of baddeleyite-type TiO2 in the shocked rocks indicates that the peak shock pressure was between 16 and 20 gigapascals, and the post-shock temperature was much lower than 500 degrees C.     

Phase Transitions Between beta and ggr (Mg, Fe)2SiO4 in the Earth's Mantle: Mechanisms and Rheological Implications

The mechanisms of the phase transformations between the spinel (gamma) and modified spinel (beta) polymorphs of Mg(2)SiO(4) have been studied experimentally between 15 and 20 gigapascals and 800 degrees to 950 degrees C. The gamma to beta transformation occurs by a shear mechanism, whereas the beta to gamma transformation involves grain-boundary nucleation and interface-controlled growth. These contrasting mechanisms are a consequence of the number of independent slip systems that are available in the respective crystal structures. This result leads to the prediction that in subduction zones and perhaps also rising plumes in the Earth's mantle, the gamma to beta transformation should be accompanied by a transient reduction in strength.     

Baddeleyite-Type High-Pressure Phase of TiO2

A high-pressure phase of TiO(2), which had been observed by shock-wave experiments and remained unresolved, has been studied by in situ x-ray diffraction. The single phase was formed at 20 gigapascals and 770 degrees C with the use of sintered-diamond multianvils; it has the same structure as baddeleyite, the stable phase of ZrO(2) at ambient conditions. The coordination number of Ti increases from six to seven across the rutile to baddeleyite transition, and the volume is reduced by approximately 9 percent.     

Monoclinic Sulfur: Heat Capacity Anomaly at 198{degrees}K Caused by Disordering of the Crystal Structure

The entropy of disorder of the idealized crystal structure of monoclinic sulfur at high temperatures is equal to the extra entropy change in the lambda-type (second order transformation type) heat capacity anomaly found at 198 degrees K. The extrapolated entropy is zero at 0 degrees K. The partially disordered crystal structure gradually becomes ordered as the temperature is lowered.     

Monoclinic hydroxyapatite

The existence of a monoclinic phase of hydroxyapatite, Ca(2)(PO(4))(4)OH, has been confirmed, by single-crystal structure analysis (weighted "reliability" factor = 3.9 percent on |F|(2)). The structure has space group P21/b, a = 9.4214(8) angstroms, b = 2a, c = 6.8814(7) angstroms, and gamma = 120 degrees , and is analogous to that of chlorapatite. The distortions from the hexagonal structure with which the monoclinic structure is pseudosymmetric are similar to those in chlorapatite, including enlargement of that triangular array of oxygen atoms in which the chlorine ion or, in hydroxyapatite, the hydroxyl hydrogen ion is approximately centered. The hydroxyapatite specimen was prepared by the conversion of a single crystal of chlorapatite in steam at 1200 degrees C, was mimetically twinned, and was approximately 37 percent monoclinic.     

Phase transformations in carbon fullerenes at high shock pressures

C(60) powders were shock-compressed quasi-isentropically and quenched from pressures in the range 10 to 110 GPa (0.1 to 1.1 Mbar). Recovered specimens were analyzed by Raman spectroscopy and optical microscopy. C(60) fullerenes are stable into the 13- to 17-GPa pressure range. The onset of a fast ( approximately 0.5 micros) reconstructive transformation to graphite occurs near 17 GPa. The graphite recovered from 27 GPa and about 600 degrees C is relatively well ordered with crystal planar domain size of about 100 A. Above 50 GPa a continuous transformation to an amorphous state is observed in recovered specimens. The fast transformation to graphite is proposed to occur by pi-electron rehybridization which initiates breakup of the ball structure and formation of the graphite structure at high density.     

Limits of microbial existence: temperature and pH

A microscopic survey made to detect the presence of bacteria in hot springs of varying temperature and pH characteristics revealed that in neutral and alkaline hot springs bacteria are found at temperatures up to the boiling point of water (92 degrees to 100 degrees C, depending on the altitude). In hot springs of increasing acidity the upper temperature limit at which bacteria are found decreases; at pH 2 to 3 the upper temperature limit is 75 degrees to 80 degrees C. Bacteria have thus been able to evolve with the ability to grow at either high temperature or high acidity, but not at both high temperature and high acidity. These results suggest that there are physicochemical limitations of the environment beyond which life is impossible.     

Transgenic mice with a reduced core body temperature have an increased life span

Reduction of core body temperature has been proposed to contribute to the increased life span and the antiaging effects conferred by calorie restriction (CR). Validation of this hypothesis has been difficult in homeotherms, primarily due to a lack of experimental models. We report that transgenic mice engineered to overexpress the uncoupling protein 2 in hypocretin neurons (Hcrt-UCP2) have elevated hypothalamic temperature. The effects of local temperature elevation on the central thermostat resulted in a 0.3 degrees to 0.5 degrees C reduction of the core body temperature. Fed ad libitum, Hcrt-UCP2 transgenic mice had the same caloric intake as their wild-type littermates but had increased energy efficiency and a greater median life span (12% increase in males; 20% increase in females). Thus, modest, sustained reduction of core body temperature prolonged life span independent of altered diet or CR.     

Superconductivity at 40 K in the Oxygen-Defect Perovskites La2-xSrxCuO4-y

Structural, magnetic, and electronic properties of compounds in the series La2-xSrx CuO4-y for 0.05 相似文献   

Vitrification temperature of water

The vitrification temperature (T(g)) of water is an elusive quantity because of the great difficulty in supercooling water sufficiently without initiating its crystallization. Water depresses the vitrification temperature of glycerol (184 degrees K) monotonously, and this property has been used for derivation of an estimate of its T(g). The result, 127 degrees +/- 4 degrees K (-146 degrees +/- 4 degrees C), is the temperature below which water presumably exists as a brittle, glassy substance.     

Tetragonal Zirconium Oxide Prepared under High Pressure

Tetragonal zirconium oxide, stable at room temperature, was synthesized at 15 to 20 kb and 12000 to 17000C. Rapid quenching produced a mixture of the monoclinic and tetragonal phases. The high-pressure specimens, when heated to 1200 degrees C in air and quenched, reverted to the all-monoclinic form.     

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.     

Tongue Cooling during Drinking: A Regulator of Water Intake in Rats

Rats that had been deprived of water for 23(1/2) hours were presented with water for 30 minutes per day. As the temperature of the water was increased from 12 degrees to 36 degrees C (body temperature), the total water intake for 30 minutes increased 71 percent. Tongue cooling during drinking appears to suppress drinking in anticipation of extracellular hydration.     

Crystal Structure of Benzene II at 25 Kilobars

Crystals of a high-pressure form of benzene (benzene 11) were grown in the diamond-anvil pressure cell at elevated temperature and pressure from the transition of solid I to solid II. X-ray precession data were obtained from a single-crystal in the high-pressure cell. At 21 degrees C and about 25 kilobars, benzene II crystallizes in the monoclinic system with a = 5.417 +/- 0.005 angstroms (S.D.), b = 5.376 +/- 0.019 angstroms, c = 7.532 +/- 0.007 angstroms, beta = 110.00 degrees +/- 0.08 degrees , space group P2(1)/ c, Pc= 1.26 grams per cubic centimeter. The crystal structure was solved by generating all possible molecular packing configurations and calculating structure factors, reliability factors, and packing energies for each configuration. This procedure produced a unique solution for the molecular packing of benzene II.     

Ultraviolet damage to bacteria and bacteriophage at low temperatures

The survival of Escherichia coli B/r WP2 (tryptophan-requiring) from ultraviolet irradiation when suspended in 0.067M phosphate buffer (pH 7) has been studied over the temperature range 22 degrees to -269 degrees C. In unfrozen suspensions there was no appreciable change in sensitivity between 22 degrees and -10 degrees C. The sensitivity in the presence of ice progressively increased by a factor of 7 when the temperature was lowered to -79 degrees C. Between -79 degrees and -196 degrees C the sensitivity decreased to less than four times the sensitivity at 22 degrees C and was not appreciably different at -269 degrees C. Evidence from experiments with bacteriophage T1 and E. coli WP2 HCR(-) (a strain unable to excise thymine dimers) indicates that a new, qualitatively different lesion, less amenable to repair, may replace the thymine dimer in E. coli irradiated at -79 degrees C.     

Environmental Control of Ovarian Development in Mosquitoes of the Culex pipiens Complex

Gonotrophic dissociation, a condition in which the ovaries remain undeveloped in female mosquitoes that have taken a full blood meal, occurs in Culex pipiens L., when incubated at low temperature (10 degrees to 15 degrees C) with short photoperiod and held at low temperature after feeding. Gonotrophic dissociation occurred sporadically in Culex quinquefasciatus Say after conditioning by low temperature, irrespective of photoperiod. Two major considerations are posed: first, the importance of gonotrophic dissociation to hibernation potential; and, second, the potential of a hibernating female mosquito to serve as a virus reservoir.     

Massive internal fracture of an amorphous polyester

When amorphious polyethylene terephthalate is subjected to a tensile load of 2 to 4 x 10(8) dynes per square centimeter wthin the approximate temperature range 40 degrees to 70 degrees C, an unusual optical effect occurs. The transparent polymer film is suddenly transformed into a brilliantly reflecting strip with the luster of silver. Extensive formation of voids accounts for the unorthodox behavior.     

AMMONIA: POSSIBLE USE FOR PRESERVING FISH

Eviscerated oil sardines (Sardinella longiceps) that have been treated with ammonia can be stored at a temperature of 25 degrees to 30 degrees C for more than 2 months without deterioration of their nutritive value. There is no measurable residue of ammonia in the final product.     

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.