Thermal Dehydration Research Articles

Vasopressin Mediates the Renal Damage Induced by Limited Fructose Rehydration in Recurrently Dehydrated Rats.

Recurrent dehydration and heat stress cause chronic kidney damage in experimental animals. The injury is exacerbated by rehydration with fructose-containing beverages. Fructose may amplify dehydration-induced injury by directly stimulating vasopressin release and also by acting as a substrate for the aldose reductase-fructokinase pathway, as both of these systems are active during dehydration. The role of vasopressin in heat stress associated injury has not to date been explored. Here we show that the amplification of renal damage mediated by fructose in thermal dehydration is mediated by vasopressin. Fructose rehydration markedly enhanced vasopressin (copeptin) levels and activation of the aldose reductase-fructokinase pathway in the kidney. Moreover, the amplification of the renal functional changes (decreased creatinine clearance and tubular injury with systemic inflammation, renal oxidative stress, and mitochondrial dysfunction) were prevented by the blockade of V1a and V2 vasopressin receptors with conivaptan. On the other hand, there are also other operative mechanisms when water is used as rehydration fluid that produce milder renal damage that is not fully corrected by vasopressin blockade. Therefore, we clearly showed evidence of the cross-talk between fructose, even at small doses, and vasopressin that interact to amplify the renal damage induced by dehydration. These data may be relevant for heat stress nephropathy as well as for other renal pathologies due to the current generalized consumption of fructose and deficient hydration habits.

Temperature- and vapor-induced reversible single-crystal-to-single-crystal transformations of three 2D/3D GdIII-organic frameworks exhibiting significant magnetocaloric effects.

By using Gd2O3, propanedioic acid (H2pda) and oxalic acid (H2ox), a new Gd-based metal-organic framework (MOF) [Gd(pda)(ox)0.5(H2O)2]n (1) has been successfully constructed and structurally characterized. Interestingly, temperature- and vapor-induced reversible single-crystal-to-single-crystal transformations occurred and two new MOFs, namely [Gd(pda)(ox)0.5(H2O)]n (1a) and [Gd(pda)(ox)0.5]n (1b), have been obtained. Complex 1 displays a two-dimensional (2D) layer structure composed of zigzag [Gd(pda)]n chains and it could also be made up of numerous Gd6 macrocycles. Thermal dehydration leads to more complicated three-dimensional (3D) 'pillar-layer' structures (1a and 1b) with the same coordination mode of pda2- anions. Magnetic studies suggest the presence of ferromagnetic couplings between the intrachain or intralayer GdIII ions and large magnetocaloric effects (MCEs) with -ΔS = 45.0 J kg-1 K-1 (1), 46.1 J kg-1 K-1 (1a) and 46.8 J kg-1 K-1 (1b) under a 7 T applied field. Therefore, the interest of 'robust magnetocaloric MOFs' is now extended to compounds showing weak ferromagnetic couplings and hence having better magnetocaloric performances for small field changes.

Dehydration of Octacyanido-Bridged NiII-WIV Framework toward Negative Thermal Expansion and Magneto-Colorimetric Switching.

An inorganic three-dimensional [NiII(H2O)2]2[WIV(CN)8]·4H2O (1) framework undergoes a single-crystal-to-single-crystal transformation upon thermal dehydration, producing a fully anhydrous phase NiII2[WIV(CN)8] (1d). The dehydration process induces changes in optical, magnetic, and thermal expansion properties. While 1 reveals typical positive thermal expansion of the crystal lattice, greenish-yellow color, and paramagnetic behavior, 1d is the first ever reported octacyanido-based solid revealing negative thermal expansion, also exhibiting a deep red color and diamagnetism. Such drastic shift in the physical properties is explained by the removal of water molecules, leaving the exclusively cyanido-bridged bimetallic network, which is accompanied by the transformation of the octahedral paramagnetic [NiII(H2O)2(NC)4]2- to the square-planar diamagnetic [NiII(NC)4]2- moieties.

A Novel Synthesis of Zinc Borates from a Zinc Oxide Precursor via Ultrasonic Irradiation.

In this study, zinc borate hydrate (Zn3B6O12 · 3.5H2O) was synthesized from zinc oxide (ZnO) and boric acid (H3BO3) via a novel method of ultrasonic irradiation. X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR) and Raman spectroscopy were used to characterize the synthesized products. Scanning electron microscopy (SEM) was used to determine the effects of reaction time and reaction temperature on the morphology of the products. Thermal dehydration kinetics were studied using thermal gravimetry and differential thermal gravimetry analysis (TG/DTA). The Doyle and Kissinger non-isothermal kinetic methods were used to analyse the TG/DTA data. The XRD results confirmed the successful synthesis of Zn3B6O12 · 3.5H2O at a range of reaction temperatures and times. Additionally, FT-IR and Raman analysis of the products identified peaks specific to zinc borate. Using the methods of Doyle and Kissinger, the activation energies of thermal dehydration of zinc borate were found to be 341.61 kJ/mol and 390.17 kJ/mol, respectively.

Influence of alternative cations distribution in AgxLi96-x-LSX on dehydration kinetics and its selective adsorption performance for N2 and O2

Adsorption characteristics of pure gases N2 and O2 on various silver exchanged low silica X-type (AgxLi96-x-LSX) zeolites were investigated. The equilibrium adsorption isotherms of N2 and O2 were measured at 273 and 298 K. Textual and structural properties of parent and resultant AgxLi96-x-LSX were characterized by XRD, BET surface area, and SEM techniques. Kinetics of their thermal dehydration were studied by exploiting thermogravimetric and differential data (TG-DTG) obtained at three heating rates (5, 10 and 15 K) using two model-free (Kissinger and Flynn-Wall-Ozawa) and one model fitting (Coats-Redfern) methods. Forty one mechanism functions were used to evaluate kinetic triplet (activation energy, frequency factor, and most probable mechanism/model) for different stages of dehydration. Results revealed that the impact of very small content of silver on the adsorption of N2 is pronounced and attributed to weak chemical bonds formed between N2 and Ag+ clusters due to strong adsorption of N2 at low pressure, whereas O2 adsorption is affected to a negligible extent. In addition, the N2/O2 adsorption selectivity shows unexpected low values for Ag87.08Li7.94Na0.98-LSX with higher Ag+ content (91.00 %), which might be due to low crystalline water content as well as Ag+ clusters located at SIII sites. N2 adsorption strongly depends on temperature as higher adsorption occurs at low temperature 273 K as compared to 298 K.

Thermodynamics of arsenates, selenites and sulfates in the oxidation zone of sulfide ores: XII. Mineral equilibria in the Cd–Se–H2O system at 25°C

Understanding the mechanisms of cadmium and selenium behavior under near-surface conditions is very important for solving certain environmental problems. The principal aim of this study is physicochemical analysis of the formation conditions of synthetic cadmium selenite CdSeO3 · H2O and experimental investigation of its thermal stability and dehydration and dissociation mechanisms. The synthesis was performed by boiling-dry aqueous solutions of cadmium nitrate and sodium selenite. The obtained samples were identified with electron microprobe and powder X-ray diffraction. Complex thermal analysis (thermogravimetry and differential scanning calorimetry) have shown that CdSeO3 · H2O is dehydrated at 177–241°C in two stages, apparently corresponding to the formation of CdSeO3 · 2/3H2O. The Eh–pH diagrams were calculated using the Geochemist’s Workbench (GWB 9.0) software package. The Eh–pH diagrams have been calculated for the Cd–Se–Н2О and Cd–Se–CO2–H2O systems for the average content of these elements in underground waters. The formation of cadmium selenite, CdSeO3 · H2O in the oxidation medium is quite possible. The existence of CdSeO3 is possible at high temperature.

Effect of Ca(II) additive on the thermal dehydration kinetics of cerium oxalate rods

Kinetics of the thermal dehydration of solid-state reaction between cerium oxalate microrods and calcium oxalate has been studied using non-isothermal TG–DTA technique. With the introduction of calcium oxalate in varying compositions, the diffusional removal of the incorporated water molecules is impeded due to the blocking action of the surface product layer and the interaction of Ca(II). The procedure of kinetic deconvolution is used as a tool for identifying the partially overlapped kinetic processes of the thermal dehydration of pure and mixed oxalates. Mixed oxalates take more complex reaction pathways for the dehydration rather than pure oxalates of calcium and cerium. The thermal dehydration of pure cerium oxalate decahydrate and calcium oxalate dihydrate occurs in two stages, whereas that of mixed oxalates occurs in three stages. The amount of activation energy needed for the removal of 10 molecules of water from pure cerium oxalate rods and its mixture with calcium oxalate was determined by the isoconversional methods such as KAS, FWO and iterative isoconversional procedure. Significant effect in the thermal stability was observed for the compositions containing lower mass% of calcium oxalate. The average values of \(E_{{{\text{a}}_{\text{i}} }}\) for each independent process of the thermal dehydration of the mixed oxalates follow the order CC4 < CC3 < CC2.

Adsorption interaction between Al–5% Pb alloy and water

The adsorption and structural features of Al–5% Pb alloy powder before and after reacting with water are analyzed. Results from studying the morphology and phase composition of the oxidation products are presented, and the specific surface area and porosity of the powders are calculated. It is shown experimentally that water treatment of Al–5% Pb alloy powder even at room temperature leads to the formation of new phases and affects the powder’s morphology. It is established that a major role in the properties of the watertreated powders is played by nanopores that form between crystallites on a particle’s surface during waterinduced oxidation and subsequent thermal dehydration.

Microporous sponge structure with copper-cobalt oxide hybrid nanobranches

A sponge structure featuring a micropore network and nanodendritic wall consisting of Cu-Co oxide core-shell like hybrid nanobranches is reported. First, microporous sponge structure with Cu-Co hybrid nanobranches was formed by hydrogen-templated electrolytic deposition. Next, Cu-Co branches were transformed to Cu-Co(OH)2 branches by selective anodic oxidation of Co. Cu-CoO branches were then obtained by subsequent thermal dehydration. During the selective anodization and subsequent dehydration of the as-deposited sample, the overall structures of micropore network and core-shell like nanodendritic branches were preserved.

Characterization and thermal decomposition of Mg2KH(AsO4)2·15H2O

In this work, we present first data on the infrared and Raman spectroscopic characteristics, thermal analysis and solid-state transformations of Mg2KH(AsO4)2·15H2O, which is a unique example of an acid salt containing dimeric units [H(AsO4)2] in its crystal structure. The infrared and Raman spectra recorded at ambient conditions have been studied, and an assignment of the observed vibrational bands has been proposed considering the crystal structure data. The thermal behavior of Mg2KH(AsO4)2·15H2O has been investigated by simultaneous TG/DTA/mass spectrometry experiments in the temperature range up to 1000 °C at different heating rates, and new data on the thermal stability and thermal dehydration of Mg2KH(AsO4)2·15H2O have been obtained. The phase composition after the dehydration processes in the temperature interval of 300–650 °C has been studied by combination of powder XRD and IR spectroscopic analyses. The spectroscopic and thermal properties of Mg2KH(AsO4)2·15H2O have been compared to those of the isostructural phosphate salt Mg2KH(PO4)2·15H2O.

Treatment of Natural Zeolites for Increasing the Sorption Capacity

This article describes the results ofthe research on determination of activity and sorption capacity of modified zeolites. Activation processes of sorbents were compared including thermal dehydration and ion-plasma treatment of zeolites. Mineralogical composition of investigated zeolites as well as the results of ion-plasma treatment on the structure of natural zeolites are presented. The obtained results have shown high effectiveness of ion-plasma treatmentof sorbents compared with thermal treatment method.

DFT-Based Simulation and Experimental Validation of the Topotactic Transformation of MgAl Layered Double Hydroxides.

The thermal topotactic transformation mechanism of MgAl layered double hydroxides (LDHs) is investigated by a combined theoretical and experimental study. Thermogravimetric differential thermal analysis (TG-DTA) results reveal that the LDH phase undergoes four key endothermic events at 230, 330, 450, and 800 °C. DFT calculations show that the LDH decomposes into CO2 and residual O atoms via a monodentate intermediate at 330 °C. At 450 °C, the metal cations almost maintain their original distribution within the LDH(001) facet during the thermal dehydration process, but migrate substantially along the c-axis direction perpendicular to the (001) facet; this indicates that the metal arrangement/dispersion in the LDH matrix is maintained two-dimensionally. A complete collapse of the layered structure occurs at 800 °C, which results in a totally disordered cation distribution and many holes in the final product. The structures of the simulated intermediates are highly consistent with the observed in situ powder XRD data for the MgAl LDH sample calcined at the corresponding temperatures. Understanding the structural topotactic transformation process of LDHs would provide helpful information for the design and preparation of metal/metal oxides functional materials derived from LDH precursors.

Influence of Ca2+ or Na+ extraframework cations on the thermal dehydration and related kinetic performance of LSX zeolite

Nitrogen adsorption performances of low-silica type X zeolites (LSX) containing Na+ or Ca2+ ions were studied and compared with Li+ ion, and their structural and thermal properties were investigated using various characterizations (XRD, TG-DTG, BET, XPS, SEM, TEM, and EDX with elemental mapping techniques). The kinetics of their thermal dehydration and decomposition was studied using thermogravimetry at three rates (5, 10, and 15K/min) of linear increase of temperature under non-isothermal heating. Two model free procedures named, Kissinger, and Flynn–Wall–Ozawa (iso-conversional) and one model fitting method called Coats–Redfern based on single TG curves, as well as 41 mechanism functions were used. The kinetic parameters (apparent activation energy E, pre-exponential factor A and model) of the three phases for each sample obtained from the non-isothermal methods were then compared with the results from iso-conversional methods this showed that they strongly depend on the selection of appropriate mechanism function and the corresponding kinetic model from the perspective of crystal structure used. The results demonstrated that the E value obtained at low temperature was lower than that at high temperature, implying that the dehydration process of physisorbed water belongs to diffusion-based control, while decomposition of bonded water (chemisorbed) belongs to kinetic-based control at high temperature. These comparisons allow us to underline the strong effect of cations in association with water and their distribution in the micropores of LSX on the N2 adsorption performance.

A metered intake of milk following exercise and thermal dehydration restores whole-body net fluid balance better than a carbohydrate-electrolyte solution or water in healthy young men.

Appropriate rehydration and nutrient intake in recovery is a key component of exercise performance. This study investigated whether the recovery of body net fluid balance (NFB) following exercise and thermal dehydration to -2 % of body mass (BM) was enhanced by a metered rate of ingestion of milk (M) compared with a carbohydrate-electrolyte solution (CE) or water (W). In randomised order, seven active men (aged 26·2 (sd 6·1) years) undertook exercise and thermal dehydration to -2 % of BM on three occasions. A metered replacement volume of M, CE or W equivalent to 150 % of the BM loss was then consumed within 2-3 h. NFB was subsequently measured for 5 h from commencement of rehydration. A higher overall NFB in M than CE (P=0·001) and W (P=0·006) was observed, with no difference between CE and W (P=0·69). After 5 h, NFB in M remained positive (+117 (sd 122) ml) compared with basal, and it was greater than W (-539 (sd 390) ml, P=0·011) but not CE (-381 (sd 460) ml, P=0·077, d=1·6). Plasma osmolality (Posm) and K remained elevated above basal in M compared with CE and W. The change in Posm was associated with circulating pre-provasopressin (r s 0·348, P<0·001), a biomarker of arginine vasopressin, but could not account fully for the augmented NFB in M compared with CE and W. These data suggest that a metered approach to fluid ingestion acts in synergy with the nutrient composition of M in the restoration of NFB following exercise and thermal dehydration.

Synthesis and properties of polyimides containing tetraphenylnaphthalene units

Aromatic polyimides (PI1x) with a tetraphenylnaphthalene unit between ether linkages were synthesized from 1,4-bis[4-(aminophenoxy)phenyl]-2,3-diphenylnaphthalene (1) and various tetracarboxylic dianhydrides by a conventional two-step procedure that included ring-opening polymerization in N-methyl-2-pyrrolidone and subsequent thermal cyclic dehydration. PI1x were characterized by X-ray diffraction, differential scanning calorimetry, thermogravimetry, and dynamic mechanical analysis. PI1x had glass transition temperatures in the range of 270–315°C and all PI1x were amorphous. The structure–property relationships of these PIs were examined and compared with those of polyimides (PI2x) from 4,4′-bis(4-aminophenoxy)biphenyl (2) and polyimides (PI3x) from 1,4-bis(4-aminophenyl)-2,3-diphenylnaphthalene (3). Water absorption and dielectric constants ( ε) of the PIs were also compared and discussed on the basis of imide content per repeating unit.

Environmental Photochemistry of Altrenogest: Photoisomerization to a Bioactive Product with Increased Environmental Persistence via Reversible Photohydration.

Despite its wide use as a veterinary pharmaceutical, environmental fate data is lacking for altrenogest, a potent synthetic progestin. Here, it is reported that direct photolysis of altrenogest under environmentally relevant conditions was extremely efficient and rapid (half-life ∼25 s). Photolysis rates (observed rate constant kobs = 2.7 ± 0.2 × 10(-2) s(-1)) were unaffected by changes in pH or temperature but were sensitive to oxygen concentrations (N2-saturated kobs = 9.10 ± 0.32 × 10(-2) s(-1); O2-saturated kobs = 1.38 ± 0.11 × 10(-2) s(-1)). The primary photoproduct was identified as an isomer formed via an internal 2 + 2 cycloaddition reaction; the triplet lifetime (8.4 ± 0.2 μs) and rate constant (8 × 10(4) s(-1)) of this reaction were measured using transient absorption spectroscopy. Subsequent characterization determined that this primary cycloaddition photoproduct undergoes photohydration. The resultant photostable secondary photoproducts are subject to thermal dehydration in dark conditions, leading to reversion to the primary cycloaddition photoproduct on a time scale of hours to days, with the photohydration and dehydration repeatable over several light/dark cycles. This dehydration reaction occurs more rapidly at higher temperatures and is also accelerated at both high and low pH values. In vitro androgen receptor (AR)-dependent gene transcriptional activation cell assays and in silico nuclear hormone receptor screening revealed that certain photoproducts retain significant androgenic activity, which has implications for exposure risks associated with the presence and cycling of altrenogest and its photoproducts in the environment.

Formation of linear polyenes in poly(vinyl alcohol) films catalyzed by phosphotungstic acid, aluminum chloride, and hydrochloric acid

Formation of linear polyenes–(CH=CH)n–via acid-catalyzed thermal dehydration of polyvinyl alcohol in 9- to 40-µm-thick films of this polymer containing hydrochloric acid, aluminum chloride, and phosphotungstic acid as dehydration catalysts was studied by electronic absorption spectroscopy. The concentration of long-chain (n ≥ 8) polyenes in films containing phosphotungstic acid is found to monotonically increase with the duration of thermal treatment of films, although the kinetics of this process is independent of film thickness. In films containing hydrochloric acid and aluminum chloride, the formation rate of polyenes with n ≥ 8 rapidly drops as film thickness decreases and the annealing time increases. As a result, at a film thickness of less than 10–12 µm, long-chain polyenes are not formed at all in these films no matter how long thermal duration is. The reason for this behavior is that hydrochloric acid catalyzing polymer dehydration in these films evaporates from the films during thermal treatment, the evaporation rate inversely depending on film thickness.

In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite, FeOH(SO4)·5H2O

The thermal dehydration process of fibroferrite, FeOH(SO4)·5H2O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO4)·4H2O, appearing at about 80 °C due to release of one interstitial H2O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.

Synthesis, characterization and thermal dehydration and degradation kinetics of chitosan Schiff bases of o-, m- and p-nitrobenzaldehyde

The chitosan Schiff bases were synthesised through the condensation reaction of chitosan with o-, m- and p-nitrobenzaldehyde (abbreviated as CSB-o, CSB-m and CSB-p) in the ratio 1:1 and were characterised by means of FTIR, UV, XRD and SEM. The thermal dehydration and degradation kinetics of all these Schiff bases were studied using different isoconversional and maximum rate (peak) methods, viz. Kissinger–Akahira–Sunose (KAS), Tang, Starink, Flynn–Wall–Ozawa (FWO) and Bosewell from DSC data and the thermal stability from TG. The activation energy values of thermal dehydration and degradation reactions obtained from isoconversional methods of FWO and Bosewell are slightly higher than that obtained from other methods. All the isoconversional and maximum rate (peak) methods yielded consistent values of E α for both the dehydration and degradation reactions and is in the order CSB-o < CSB-m < CSB-p. The Schiff bases observed (from TG) the same order of thermal stability.

Insight into Hydrogen Bonding of Uranyl Hydroxide Layers and Capsules by Use of 1H Magic-Angle Spinning NMR Spectroscopy

Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO2(OH)2] (α-UOH) and hydrated uranyl hydroxide [(UO2)4O(OH)6·5H2O (metaschoepite). For the metaschoepite material, proton resonances of the μ2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H–1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. These NMR correlations allowed characterization of local hydrogen-bond environments in uranyl U24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.