Hydrothermal Instability Of Thermocapillary Convection In Large-Prandtl-Number Liquid Bridges Under Microgravity

Linear stability analysis was performed to study the mechanism of transition of thermocapillary convection in liquid bridges with liquid volume ratios ranging from 0.4 to 1.2, aspect ratio of 0.75 and Prandtl number of 100. 2-D governing equations were solved to obtain the steady axi-symmetric basic flow and temperature distributions. 3-D perturbation equations were discretized at the collocation grid points using the Chebyshev-collocation method. Eigenvalues and eigenfunctions were obtained by using the Q-R. method. The predicted critical Marangoni numbers and critical frequencies were compared with data from space experiments. The disturbance of the temperature distribution on the free surface causes the onset of oscillatory convection. It is shown that the origin of instability is related to the hydrothermal origin for convections in large-Prandtl-number liquid bridges. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.

A unified strategy to ent-kauranoid natural products : total syntheses of (–)-maoecrystal Z, (–)-trichorabdal A, and (–)-longikaurin E

The diterpenoid constituents of the Isodon plants have attracted reasearchers interested in both their chemical structures and biological properties for more than a half-century. In recent years, the isolations of new members displaying previously unprecedented ring systems and highly selective biological properties have piqued interest from the synthetic community in this class of natural products.

Reported herein is the first total synthesis of such a recently isolated diterpenoid, (–)-maoecrystal Z. The principal transformations implemented in this synthesis include two highly diastereoselective radical cyclization reactions: a Sm^(II)-mediated reductive cascade cyclization, which forms two rings and establishes four new stereocenters in a single step, and a Ti^(III)-mediated reductive epoxide-acrylate coupling that yields a functionalized spirolactone product, which forms a core bicycle of maoecrystal Z.

The preparation of two additional ent-kauranoid natural products, (–)-trichorabdal A and (–)-longikaurin E, is also described from a derivative of this key spirolactone. These syntheses are additionally enabled by the palladium-mediated oxidative cyclization reaction of a silyl ketene acetal precursor that is used to install the bridgehead all-carbon quaternary stereocenter and bicyclo[3.2.1]octane present in each natural product. These studies have established a synthetic relationship among three architecturally distinct ent-kaurane diterpenoids and have forged a path for the preparation of interesting unnatural ent-kauranoid structural analogs for more thorough biological study.

The development of an asymmetric palladium-catalyzed conjugate addition and its application toward the total syntheses of taiwaniaquinoid natural products

The asymmetric synthesis of quaternary stereocenters remains a challenging problem in organic synthesis. Past work from the Stoltz laboratory has resulted in methodology to install quaternary stereocenters α- or γ- to carbonyl compounds. Thus, the asymmetric synthesis of β-quaternary stereocenters was a desirable objective, and was accomplished by engineering the palladium-catalyzed addition of arylmetal organometallic reagents to α,β-unsaturated conjugate acceptors.

Herein, we described the rational design of a palladium-catalyzed conjugate addition reactions utilizing a catalyst derived from palladium(II) trifluoroacetate and pyridinooxazole ligands. This reaction is highly tolerant of protic solvents and oxygen atmosphere, making it a practical and operationally simple reaction. The mild conditions facilitate a remarkably high functional group tolerance, including carbonyls, halogens, and fluorinated functional groups. Furthermore, the reaction catalyzed conjugate additions with high enantioselectivity with conjugate acceptors of 5-, 6-, and 7-membered ring sizes. Extension of the methodology toward the asymmetric synthesis of flavanone products is presented, as well.

A computational and experimental investigation into the reaction mechanism provided a stereochemical model for enantioinduction, whereby the α-methylene protons adjacent the enone carbonyl clashes with the tert-butyl groups of the chiral ligand. Additionally, it was found that the addition of water and ammonium hexafluorophosphate significantly increases the reaction rate without sacrificing enantioselectivity. The synergistic effects of these additives allowed for the reaction to proceed at a lower temperature, and thus facilitated expansion of the substrate scope to sensitive functional groups such as protic amides and aryl bromides. Investigations into a scale-up synthesis of the chiral ligand (S)-tert-butylPyOx are also presented. This three-step synthetic route allowed for synthesis of the target compound of greater than 10 g scale.

Finally, the application of the newly developed conjugate addition reaction toward the synthesis of the taiwaniaquinoid class of terpenoid natural products is discussed. The conjugate addition reaction formed the key benzylic quaternary stereocenter in high enantioselectivity, joining together the majority of the carbons in the taiwaniaquinoid scaffold. Efforts toward the synthesis of the B-ring are presented.

Applications of a Concise and General Strategy for the Syntheses of Transtaganolide and Basiliolide Natural Products

Herein are described the total syntheses of all members of the transtaganolide and basiliolide natural product family. Utilitzation of an Ireland–Claisen rearrangement/Diels–Alder cycloaddition cascade (ICR/DA) allowed for rapid assembly of the transtaganolide and basiliolide oxabicyclo[2.2.2]octane core. This methodology is general and was applicable to all members of the natural product family.

A brief introduction outlines all the synthetic progress previously disclosed by Lee, Dudley, and Johansson. This also includes the initial syntheses of transtaganolides C and D, as well as basiliolide B and epi-basiliolide B accomplished by Stoltz in 2011. Lastly, we discuss our racemic synthesis of basililide C and epi-basiliolide C, which utilized an ICR/DA cascade to constuct the oxabicyclo[2.2.2]octane core and formal [5+2] annulation to form the ketene-acetal containing 7-membered C-ring.

Next, we describe a strategy for an asymmetric ICR/DA cascade, by incorporation of a chiral silane directing group. This allowed for enantioselective construction of the C8 all-carbon quaternary center formed in the Ireland–Claisen rearrangement. Furthermore, a single hydride reduction and subsequent translactonization of a C4 methylester bearing oxabicyclo[2.2.2]octane core demonstrated a viable strategy for the desired skeletal rearrangement to obtain pentacyclic transtaganolides A and B. Application of the asymmetric strategy culminated in the total syntheses of (–)-transtaganolide A, (+)-transtaganolide B, (+)-transtaganolide C, and (–)-transtaganolide D. Comparison of the optical rotation data of the synthetically derived transtaganolides to that from the isolated counterparts has overarching biosynthetic implications which are discussed.

Lastly, improvement to the formal [5+2] annulation strategy is described. Negishi cross-coupling of methoxyethynyl zinc chloride using a palladium Xantphos catalyst is optimized for iodo-cyclohexene. Application of this technology to an iodo-pyrone geranyl ester allowed for formation and isolation of the eneyne product. Hydration of the enenye product forms natural metabolite basiliopyrone. Furthermore, the eneyne product can undergo an ICR/DA cascade and form transtaganolides C and D in a single step from an achiral monocyclic precursor.

Mechanism of mass transfer in the formation of hydrothermal deposits of sulphides [Translation from: Trudy Inst.Geol.rudn.Mesterozh. 16, 80 [pages 44-46 ”Solubility of sulphides of iron” only], 1958]

This partial translation of the original paper provides the summary of this study of the mechanism of mass transfer in the formation of hydrothermal deposits of sulphides. For determining the solubility of sulphides of iron, the radioactive isotope Fe59 was used. The solubility of two sulphides was determined.

Hydrothermal experiments on the thermal stability of amino substances in sediments

Aspartic acid, threonine, serine and other thermally unstable amino acids have been found in fine-grained elastic sediments of advanced geologic age. The presence of these compounds in ancient sediments conflicts with experimental data determined for their simple thermal decomposition.

Recent and Late Miocene sediments and their humic acid extracts, known to contain essentially complete suites of amino acids, were heated with H₂O in a bomb at temperatures up to 500°C in order to compare the thermal decomposition characteristics of the sedimentary amino compounds.

Most of the amino acids found in protein hydrolyzates are obtained from the Miocene rock in amounts 10 to 100 times less than from the Recent sediment. The two unheated humic acids are rather similar despite their great age difference. The Miocene rock appears uncontaminated by Recent carbon.

Yields of amino acids generally decline in the heated Recent sediment. Some amino compounds apparently increase with heating time in the Miocene rock.

Relative thermal stabilities of the amino acids in sediments are generally similar to those determined using pure aqueous solutions. The relative thermal stabilities of glutamic acid, glycine, and phenylalanine vary in the Recent sediment but are uniform in the Miocene rock.

Amino acids may occur in both proteins and humic complexes in the Recent sediment, while they are probably only present in stabilized organic substances in the Miocene rock. Thermal decomposition of protein amino acids may be affected by surface catalysis in the Recent sediment. The apparent activation energy for the decomposition of alanine in this sediment is 8400 calories per mole. Yields of amino compounds from the heated sediments are not affected by thermal decomposition only.

Amino acids in sediments may only be useful for geothermometry in a very general way.

A better picture of the amino acid content of older sedimentary rocks may be obtained if these sediments are heated in a bomb with H₂O at temperatures around 150°C prior to HCl hydrolysis.

Leucine-isoleucine ratios may prove to be useful as indicators of amino acid sources or for evaluating the fractionation of these substances during diagenesis. Leucine-isoleucine ratios of the Recent and Miocene sediments and humic acids are identical. The humic acids may have a continental source.

The carbon-nitrogen and carbon-hydrogen ratios of sediments and humic acids increase with heating time and temperature. Ratios comparable to those in some kerogens are found in the severely heated Miocene sediment and humic acid.

Growth of composite sapphire/Ti : sapphire by the hydrothermal method

Composite sapphire/Ti:sapphire crystals for high-power laser application were grown by the hydrothermal method. The results of the X-ray rocking curve analysis indicate high crystalline quality of the surface Al2O3 material. The strong bonding between the overgrown Al2O3 and seed Ti:Al2O3 crystals is indispensable for withstanding high thermal stresses produced by intense optical pumping. The optical loss at the boundary of the composite crystal is considerably low, indicating the lack of scattering centers. (c) 2005 Elsevier B.V. All rights reserved.

Low-temperature hydrothermal growth of oriented [0001] ZnO film

Well-aligned ZnO films have been successfully prepared by using low-temperature hydrothermal approach on (0001) sapphire substrates that were pre-coated with a ZnO nano-layer by dip-coating. The characterizations of scanning electron microscopy (SEM) and X-ray diffraction (XRD) indicate that the ZnO films consist of hexagonal rods that grow along the c axis based on the sapphire substrates. It is found that the size of ZnO rods can be adjusted by an aqueous solution with some methenamine. (c) 2006 Elsevier B.V. All rights reserved.

Hydrothermal growth and characterization of ZnO crystals

ZnO crystals with dimensions of 30 x 38 x 8 turn 3 have been grown by the hydrothermal method using a mixed solution of KOH, LiOH and H2O2. The growing rates for +c(0001) and -c(000 (1) over bar) were 0.17 and 0.09 mm/day, respectively. The crystal color was very light green for +c sector and dark brown for -c sector. For the +c sector, the resistivity at room temperature was 80 0 cm, the carrier concentration was about 10(4)/cm(3), and the mobility was about 100 cm(2)/Vs. The full-width at half-maximum (FWHM) of double axis X-ray rocking curve for the polished Zn face cut from +c sector was 45 arcsec. The photoluminescence (PL) spectrum and the absorption spectrum of +c part of the crystals at room temperature were also reported and discussed in this paper. (c) 2008 Elsevier B.V. All rights reserved.

Hydrothermal Synthesis and Study of Inorganic-Organic Hybrid Vanadate of Nickel(II) Coordination Complex with Pyrazine, Ni3(C4H4N2)3(V8O23)

Artículo científico: postprint

Mild Hydrothermal Synthesis, Crystal Structure, Thermal Behavior, Spectroscopic and Magnetic Properties of (NH4)0.80Li0.20[Fe(AsO4)F]

postprint

Near-ultraviolet zinc oxide nanowire sensor using low temperature hydrothermal growth.

Two near-ultraviolet (UV) sensors based on solution-grown zinc oxide (ZnO) nanowires (NWs) which are only sensitive to photo-excitation at or below 400 nm wavelength have been fabricated and characterized. Both devices keep all processing steps, including nanowire growth, under 100 °C for compatibility with a wide variety of substrates. The first device type uses a single optical lithography step process to allow simultaneous in situ horizontal NW growth from solution and creation of symmetric ohmic contacts to the nanowires. The second device type uses a two-mask optical lithography process to create asymmetric ohmic and Schottky contacts. For the symmetric ohmic contacts, at a voltage bias of 1 V across the device, we observed a 29-fold increase in current in comparison to dark current when the NWs were photo-excited by a 400 nm light-emitting diode (LED) at 0.15 mW cm(-2) with a relaxation time constant (τ) ranging from 50 to 555 s. For the asymmetric ohmic and Schottky contacts under 400 nm excitation, τ is measured between 0.5 and 1.4 s over varying time internals, which is ~2 orders of magnitude faster than the devices using symmetric ohmic contacts.

Syntheses, crystallographic and magnetic properties of Nd3Fe29-xCrx and other associated compounds

A systematic study of syntheses and magnetic properties of the Nd-3 Fe29-xCrx (x=4.5, 4.7, 5.0, and 5.5) compounds has been performed. The single-phase compounds of Nd3Fe29-xCrx can be formed in the range 4.5 less than or equal to x less than or equal to 5.5. The Curie temperature Tc, the saturation magnetization M-S at 4.2 K, the anisotropy field H-A at 4.2 K and room temperature, and the intra-sublattice exchange coupling parameter j(FeFe) at 4.2 K for the Nd3Fe29-xCrx compounds decrease with increasing Cr composition from x=4.5 to 5.5, respectively. Nitrogenation and carbonation, unlike hydrogenation, result mainly in improvements of the Curie temperature, the saturation magnetization and the anisotropy field at 4.2 K and room temperature for the Nd3Fe29-xCrx compounds compared with their parent compounds.

Synthesis of novel hexagon SnO2 nanosheets in ethanol/water solution by hydrothermal process

The novel hexagon SnO2 nanosheets are successfully synthesized in ethanol/water solution by hydrothermal process. The samples are characterized by X-ray diffraction (XRD), infrared ray (IR) and transmission electron microscopy (TEM). By changing the reaction conditions, the size and the morphology can be controlled. Comparison experiments show that when the temperature increased from 140 degrees C to 180 degrees C, the edge length of the hexagon nanoparticles increases from 300-450 nm to 700-900 nm. On the other hand, by adjusting the ratios of water to ethanol from 2 to 0.5, SnO2 nanoparticles with different morphologies of triangle and sphere are obtained. When the concentration of NaOH is increased from 0.15 M to 0.30 M, a hollow ring structure can be obtained. (c) 2006 Elsevier B.V. All rights reserved.