Use of the diffusive gradients in thin films technique (DGT) with various diffusive gels for characterization of sewage sludge-contaminated soils

The diffusive gradients in thin film technique (DGT) was used for characterization of South Moravian arable soils (sampling sites Zlín, Tuřany, and Chrlice) amended by sewage sludge in the 1980s. Two types of polyacrylamide diffusive gel with different pore size (APA gels—cross-linked with agarose and RG gels—cross-linked with bis-acrylamide) were employed. The (bio)available parts of Cd, Cu, and Ni and the proportions of inorganically and organically complexed species of these metals were assessed. The degree of metal resupply from the soil solid phase to the soil solution was also determined. Metal concentrations obtained by the DGT technique were lower by almost 4 to 5 orders of magnitude in comparison with those obtained by extraction with aqua regia. DGT concentrations of metals were also lower by approximately 1 to 2 orders of magnitude in comparison with those obtained by extraction with sodium nitrate (commonly used for assessment of the (bio)available part of metals). Results obtained by DGT measurement were expected to be closer to the actual content of available metal species than results obtained by extraction with sodium nitrate. Using RG gels together with APA gels provided resolution of inorganically and organically complexed metal species and their proportional representation. Inorganic metal species (particles smaller than 1 nm) formed a predominant part of assessed metal content in all studied soil samples and horizons. However, there was the exception of the cadmium content in the middle profile of Chrlice sandy soil sample. Ratio R values indicated that resupply of Cd, Cu, and Ni from the solid phase to the soil solution varied for individual soil samples and individual depth profiles. Mobile and labile species of Cd, Cu, and Ni were much more closely related to upper rather than deeper horizons. This observation correlates very well with the mechanical treatment and amendment of the studied soils.     

Experimental study of pool temperature effects on nucleate pool boiling

Nucleate pool boiling experiments with constant wall temperature were performed using pure R113 for subcooled, saturated, and superheated pool conditions. A microscale heater array and Wheatstone bridge circuits were used to maintain the constant wall temperature and to measure the instantaneous heat flow rate accurately with high temporal and spatial resolutions. Images of bubble growth were taken at 5000 frames per second using a high-speed CCD camera synchronized with the heat flow rate measurements. The bubble geometry was obtained from the captured bubble images. The effect of the pool conditions on the bubble growth behavior was analyzed using dimensionless parameters for the initial and thermal growth regions. The effect of the pool conditions on the heat flow rate behavior was also examined. The bubble growth behaviors during subcooled, saturated, and superheated pool boiling were analyzed using a modified Jakob number that we newly defined. Dimensionless time and bubble radius parameters with the modified Jakob number characterized the bubble growth behavior well. These phenomena require further analysis for various pool temperature conditions, and this study will provide good experimental data with precise constant wall temperature boundary condition for such works.     

Cobalt‐Mediated Radical Polymerization of Vinyl Acetate and Acrylonitrile in Supercritical Carbon Dioxide

Cobalt‐mediated radical polymerization (CMRP) of vinyl acetate (VAc) is successfully achieved in supercritical carbon dioxide (scCO₂). CMRP of VAc is conducted using an alkyl‐cobalt(III) adduct that is soluble in scCO₂. Kinetics studies coupled to visual observations of the polymerization medium highlight that the melt viscosity and PVAc molar mass (M_n) are key parameters that affect the CMRP in scCO₂. It is noticed that CMRP is controlled for M_n up to 10 000 g mol⁻¹, but loss of control is progressively observed for higher molar masses when PVAc precipitates in the polymerization medium. Low molar mass PVAc macroinitiator, prepared by CMRP in scCO₂, is then successfully used to initiate the acrylonitrile polymerization. PVAc‐b‐PAN block copolymer is collected as a free flowing powder at the end of the process although the dispersity of the copolymer increases with the reaction time. Although optimization is required to decrease the dispersity of the polymer formed, this CMRP process opens new perspectives for macromolecular engineering in scCO₂ without the utilization of fluorinated comonomers or organic solvents.

     

Single bubble growth in saturated pool boiling on a constant wall temperature surface

Nucleate pool boiling experiments with constant wall temperatures were performed using R11 and R113 for saturated pool boiling conditions. A microscale heater array and Wheatstone bridge circuits were used to maintain a constant wall temperature condition and to obtain measurements with high temporal and spatial resolution. Accurate heat flow rate data were obtained from microscale heater array by controlling the surface conditions at a high temporal resolution. Images of the bubble growth were captured using a high-speed CCD camera synchronized with the heat flow rate measurements. The geometry of the bubble was obtained from the images. In the asymptotic growth region, the bubble showed a growth rate that was proportional to t^1/5, which was slower than the growth rate proposed in previous analytical analyses. The bubble growth behavior was analyzed using a new dimensionless parameter to permit comparisons with previous results at the same scale. The comparisons showed good agreement in the asymptotic growth region. A non-dimensional correlation for the bubble radius that can predict the bubble growth and the heat flow rate simultaneously, was suggested. The required heat flow rate for the volume change of the observed bubble was estimated to be larger than the instantaneous heat flow rate measured from the wall. Heat, other than the instantaneous heat supplied from the wall, is estimated to be transferred through the interface between bubble and liquid, even with saturated pool conditions. This phenomenon under a saturated pool condition needs to be analyzed and the data from this study can supply the good experimental data with the precise boundary condition (constant wall temperature).     

Phospholipase D activates HIF-1-VEGF pathway via phosphatidic acid

Growth factor-stimulated phospholipase D (PLD) catalyzes the hydrolysis of phosphatidylcholine (PC), generating phosphatidic acid (PA) which may act as a second messenger during cell proliferation and survival. Therefore, PLD is believed to play an important role in tumorigenesis. In this study, a potential mechanism for PLD-mediated tumorigenesis was explored. Ectopic expression of PLD1 or PLD2 in human glioma U87 cells increased the expression of hypoxia-inducible factor-1α (HIF-1α) protein. PLD-induced HIF-1 activation led to the secretion of vascular endothelial growth factor (VEGF), a HIF-1 target gene involved in tumorigenesis. PLD induction of HIF-1α was significantly attenuated by 1-butanol which blocks PA production by PLD, and PA per se was able to elevate HIF-1α protein level. Inhibition of mTOR, a PA-responsive kinase, reduced the levels of HIF-1α and VEGF in PLD-overexpressed cells. Epidermal growth factor activated PLD and increased the levels of HIF-1α and VEGF in U87 cells. A specific PLD inhibitor abolished expression of HIF-1α and secretion of VEGF. PLD may utilize HIF-1-VEGF pathway for PLD-mediated tumor cell proliferation and survival.     

Selective Capture of Carbon Dioxide under Humid Conditions by Hydrophobic Chabazite‐Type Zeolitic Imidazolate Frameworks

Hydrophobic zeolitic imidazolate frameworks (ZIFs) with the chabazite ( CHA ) topology are synthesized by incorporating two distinct imidazolate links. Zn(2‐mIm)_0.86(bbIm)_1.14 (ZIF‐300), Zn(2‐mIm)_0.94(cbIm)_1.06 (ZIF‐301), and Zn(2‐mIm)_0.67(mbIm)_1.33 (ZIF‐302), where 2‐mIm=2‐methylimidazolate, bbIm=5(6)‐bromobenzimidazolate, cbIm=5(6)‐chlorobenzimidazolate, and mbIm=5(6)‐methylbenzimidazolate, were prepared by reacting zinc nitrate tetrahydrate and 2‐mIm with the respective bIm link in a mixture of N,N‐dimethylformamide (DMF) and water. Their structures were determined by single‐crystal X‐ray diffraction and their permanent porosity shown. All of these structures are hydrophobic as confirmed by water adsorption isotherms. All three ZIFs are equally effective at the dynamic separation of CO₂ from N₂ under both dry and humid conditions without any loss of performance over three cycles and can be regenerated simply by using a N₂ flow at ambient temperature.     

Simulation study of two-dimensional phase transitions of argon on graphite surface and in slit micropores

Molecular simulation has been increasingly used in the analysis and modeling of gas adsorption on open surfaces and in porous materials because greater insight could be gained from such a study. In case of homogeneous surfaces or pore walls the adsorption behavior is often complicated by the order–disorder transition. It is shown in our previous publications (Ustinov and Do, Langmuir 28:9543–9553, 2012a; Ustinov and Do, Adsorption 19:291–304, 2013) that once an ordered molecular layer has been formed on the surface, the lattice constant depends on the simulation box size, which requires adjusting the box dimensions parallel to the surface for each value of loading. It was shown that this can be accomplished with the Gibbs–Duhem equation, which results in decreasing lattice constant with an increase of the amount adsorbed. The same feature is expected to be valid for gas adsorption in narrow pores, but this has not been analyzed in the literature. This study aims at an extension of our approach to adsorption in slit graphitic pores using kinetic Monte Carlo method (Ustinov and Do, J Colloid Interface Sci 366:216–223, 2012b). The emphasis rests on the thermodynamic analysis of the two-dimensional (2D) ordering transition and state of the ordered phase; if the ordered phase exists in narrow slit pores, simulation with constant volume box always leads to erroneous results, for example, seemingly incompressible adsorbed phase. We proposed a new approach that allows for modeling thermodynamically consistent adsorption isotherms, which can be used as a basis for further refinement of the pore size distribution analysis of nanoporous materials.     

Composition of essential oils of four <Emphasis Type="Italic">Hedychium</Emphasis>species from Vietnam

Background

Vietnam is a country blessed with many medicinal plants widely used as food and for medicinal purposes, and they contain a host of active substances that contribute to health. However, the analysis of chemical constituents of these plant species has not been subject of literature discussion.

Results

In this study, the chemical compositions of essential oils of four Hedychium species, obtained by hydrodistillation, were determined by means of gas chromatography-flame ionization detector (GC-FID) and gas chromatography–mass spectrometry (GC-MS) techniques. Individually, α-pinene (52.5%) and β-pinene (31.8%) were present in the leaf oil of Hedychium stenopetalum Lodd., while linalool (45.2%), (E)-nerolidol (8.7%) and α-pinene (5.0%) were identified in the root. The leaf of Hedychium coronarium J. König was characterized by α-pinene (20.0%), linalool (15.8%), 1,8-cineole (10.7%), α-pinene (10.1%) and α-terpineol (8.6%); while α-pinene (23.6%), α-humulene (17.1%) and β-caryophyllene (13.0%) were identified in the root. Hedychium flavum Roxb., gave oil whose major compounds were α-pinene (22.5%), α-humulene (15.7%) and β-caryophyllene (10.4%) in the leaf; α-humulene (18.9%), β-caryophyllene (11.8%) and α-pinene (11.2%) in the stem, as well as α-pinene (21.8%), linalool (17.5%) and 1,8-cineole (13.5%) in the root. The main constituents of Hedychium ellipticum Buch.-Ham. ex Smith were (E)-nerolidol (15.9%), α-pinene (11.8%) and bornyl acetate (9.2%) in the leaf with 1,8-cineole (40.8%), α-pinene (18.3%) and α-pinene (11.0%) occurring in the root.

Conclusions

Ubiquitous monoterpenes and sesquiterpenes were identified as characteristic markers for Hedychium species. This work is of great importance for the evaluation of Hedychium essential oils grown in Vietnam.

     

The Many Roles of Quantum Chemical Predictions in Synthetic Organic Chemistry

This account discusses representative case studies for various applications of quantum chemical calculations in synthetic organic chemistry. These include confirmation of target structures, methodology development, and catalyst design. These examples demonstrate how predictions from quantum chemical calculations can be utilized to streamline synthetic efforts.