Experimental evidence of the cavity theory of sorption-desorption hysteresis by a study of the effect of electric discharge on entrapped water in silica gel

With the use of the quartz fiber spring balance, sorptions and desorptions of water on silica gel at 30°C were studied and the permanent and reproducible hysteresis loop was obtained. At different points on the desorption curve forming the loop, the gel was subjected to high tension glow electric discharge. As a result of the electric discharge, the gel at any point on the desorption curve shifts to a corresponding point on the sorption curve. This is due to the release from the cavities of gel of the entrapped water held in a metastable state. The electric discharge has no effect on the gel at different points on portions of the desorption curve which coincide with the sorption curve and also on the sorption curve itself, indicating the absence of entrapped water in the gel in these regions. The results afford direct experimental evidence of the reality of the cavity theory of sorption-desorption hysteresis.

H-bonding in entrapped water in poly(o-methoxyaniline): Results from a differential scanning calorimetry study

Differential scanning calorimetry (DSC) was used to investigate entrapped water in poly(o-methoxyaniline) (POMA) in powder form. Two endothermic peaks were attributed to removal of water molecules that were adsorbed with distinct energies. By obtaining thermograms at various heating rates, we succeeded in applying Kissinger's approaches to estimate activation energies for the water adsorbed. The values obtained were ca. 25 and 53 kJ/mol, which correspond to H-bonding interactions, probably at the amine and imine centers of POMA, respectively. (C) 2005 Elsevier B.V. All rights reserved.

Hydrophobic Peptide Channels and Encapsulated Water Wires

Peptide nanotubes with filled and empty pores and close-packed structures are formed in closely related pentapeptides. Enantiomorphic sequences, Boc-(D)Pro-Aib-Xxx-Aib-Val-OMe (Xxx = Leu, 1; Val, 2; Ala, 3; Phe, 4) and Boc-Pro-Aib-(D)Xxx-Aib-(D)Val-OMe ((XXX)-X-D = (D)Leu, 5; (D)Val, 6; (D)Ala, 7; (D)Phe, 8), yield molecular structures with a very similar backbone conformation but varied packing patterns in crystals. Peptides 1, 2, 5, and 6 show tubular structures with the molecules self-assembling along the crystallographic six-fold axis (c-axis) and revealing a honeycomb arrangement laterally (ab plane). Two forms of entrapped water wires have been characterized in 2: 2a with d(O center dot center dot center dot O) = 2.6 angstrom and 2b with d(O center dot center dot center dot O) = 3.5 angstrom. The latter is observed in 6 (6a) also. A polymorphic form of 6 (6b), grown from a solution of methanol-water, was observed to crystallize in a monoclinic system as a close-packed structure. Single-file water wire arrangements encapsulated inside hydrophobic channels formed by peptide nanotubes could be established by modeling the published structures in the cases of a cyclic peptide and a dipeptide. In all the entrapped water wires, each water molecule is involved in a hydrogen bond with a previous and succeeding water molecule. The O-H group of the water not involved in any hydrogen bond does not seem to be involved in an energetically significant interaction with the nanotube interior, a general feature of the one-dimensional water wires encapsulated in hydrophobic environements. Water wires in hydrophobic channels are contrasted with the single-file arrangements in amphipathic channels formed by aquaporins.

Cation-templated 2-D Mn(II)-oxalate framework with an acyclic tetrameric water cluster

The single-crystal X-ray structure of a cation-templated manganese-oxalate coordination polymer [NH(C2H5)(3)][Mn-2(ox)(3)]center dot(5H(2)O)] (1) is reported. In 1, triethylammonium cation is entrapped between the cavities of 2-D honeycomb layers constructed by oxalate and water. The acyclic tetrameric water clusters and discrete water assemble the parallel 2-D honeycomb oxalate layers via an intricate array of hydrogen bonds into an overall 3-D network. The magnetic susceptibility, with and without the water cluster, are reported with infrared and EPR studies.

Sol-gel-entrapped nano silver catalysts-correlation between active silver species and catalytic behavior

Silver colloids prepared by reducing AgNO3 in aqueous solution with sodium citrate were embedded in alumina following two different preparation procedures resulting in samples containing 3 and 5 wt.% silver. Characterization of these materials using TEM. XPS, XAES, CP/MAS NMR, XRD, and adsorption-desorption isotherms of nitrogen showed that embedding the pre-prepared silver colloids into the alumina via the sol-gel procedure preserved the particle size of silver. However, as XAES demonstrates, the catalysts prepared in a sol-gel with a lower amount of water led to embedded colloids with a higher population of Ag+ species. The catalytic behaviors of the resultant catalysts were well correlated with the concentration of these species. Thus, the active silver species of the catalysts containing more Ag+ species selectively converts NO to N-2. However, subsequent thermal aging leads to an enhancement of the conversion of NO parallel to slight alteration of the selectivity with the appearance of low amounts of N2O despite an increase of Ag+ species. Accordingly, an optimal surface Ag-0/Ag+ ratio is probably needed, independently of the size of silver particles. It was found that this optimal ratio strongly depends on the operating conditions during the synthesis route. (C) 2010 Elsevier Inc. All rights reserved.

Molar gas ratios and stable oxygen and nitrogen isotopes of air entrapped in ice, North America

The molar ratios of atmospheric gases change during dissolution in water due to differences in their relative solubilities. We exploited this characteristic to develop a tool to clarify the origin of ice formations in permafrost regions. Extracted from ice, molar gas ratios can distinguish buried glacier ice from intrasedimental ground ice formed by freezing groundwaters. An extraction line was built to isolate gases from ice by melting and trapping with liquid He, followed by analysis of N2, O2, Ar, 18O-O2 and 15N-N2, by continuous flow mass spectrometry. The method was tested using glacier ice, aufeis ice (river icing) and intrasedimental ground ice from sites in the Canadian Arctic. O2/Ar and N2/Ar ratios clearly distinguish between atmospheric gas in glacial ice and gases from intrasedimental ground ice, which are exsolved from freezing water. 615NN2 and 618OO2 in glacier ice, aufeis ice and intrasedimental ground ice do not show clear distinguishing trends as they are affected by various physical processes during formation such as gravitational settling, excess air addition, mixing with snow pack, and respiration.

alpha- and gamma-Hexachlorocyclohexane concentrations in brine, bulk sea-ice, water and air during a CCGS Amundsen cruise to the Canadian western Arctic

We used holes augered partially into first-year sea ice (sumps) to determine a- and g-HCH concentrations in sea-ice brine. The overwintering of the CCGS Amundsen in the Canadian western Arctic, as part of the Circumpolar Flaw Lead (CFL) System Study, provided the circumstances to allow brine to accumulate in sumps sufficiently to test the methodology. We show, for the first time, that as much as 50% of total HCHs in seawater can become entrapped within the ice crystal matrix. On average, in the winter first-year sea ice HCH brine concentrations reached 4.013 ± 0.307 ng/L and 0.423 ± 0.013 ng/L for the a- and g-isomer, respectively. In the spring, HCHs decreased gradually with time, with increasing brine volume fraction and decreasing brine salinity. These decreasing concentrations could be accounted for by both the dilution with the ice crystal matrix and under-ice seawater. We propose that the former process plays a more significant role considering brine volume fractions calculated in this study were below 20%. Levels of HCHs in the brine exceed under-ice water concentrations by approximately a factor of 3, a circumstance suggesting that the brine ecosystem has been, and continues to be, the most exposed to HCHs.

Water source utilization and foliar nutrient status differs between upland and flooded plant communities in wetland tree islands

Tree islands in the Everglades wetlands are centers of biodiversity and targets of restoration, yet little is known about the pattern of water source utilization by the constituent woody plant communities: upland hammocks and flooded swamp forests. Two potential water sources exist: (1) entrapped rainwater in the vadose zone of the organic soil (referred to as upland soil water), that becomes enriched in phosphorus, and (2) phosphorus-poor groundwater/surface water (referred to as regional water). Using natural stable isotope abundance as a tracer, we observed that hammock plants used upland soil water in the wet season and shifted to regional water uptake in the dry season, while swamp forest plants used regional water throughout the year. Consistent with the previously observed phosphorus concentrations of the two water sources, hammock plants had a greater annual mean foliar phosphorus concentration over swamp forest plants, thereby supporting the idea that tree island hammocks are islands of high phosphorus concentrations in the oligotrophic Everglades. Foliar nitrogen levels in swamp forest plants were higher than those of hammock plants. Linking water sources with foliar nutrient concentrations can indicate nutrient sources and periods of nutrient uptake, thereby linking hydrology with the nutrient regimes of different plant communities in wetland ecosystems. Our results are consistent with the hypotheses that (1) over long periods, upland tree island communities incrementally increase their nutrient concentration by incorporating marsh nutrients through transpiration seasonally, and (2) small differences in micro-topography in a wetland ecosystem can lead to large differences in water and nutrient cycles.