Aqueous Urea Research Articles

Extreme enthalpy‒entropy compensation in the dimerization of small solutes in aqueous solution.

This communication summarizes findings from the earliest encounters with extreme enthalpy‒entropy compensation, a phenomenon first detected in the 1950s by a reappraisal of isopiestic and calorimetric measurements on aqueous urea solutions in terms of solute self-association. Because concurrent studies of carboxylic acid association were confined to measurement of the equilibrium constant by conductance, IR spectrophotometry or potentiometric titration measurements, temperature-independence of the dimerization constant was mistakenly taken to signify a value of zero for Δ instead of (Δ ‒TΔ ). In those studies of small-solute self-association the extreme enthalpy‒entropy compensation was reflecting the action of water as a reactant whose hydroxyl groups were competing for the solute carbonyl involved in self-association. Such action gives rise to a positive temperature dependence of Δ that could well be operating in concert with that responsible for the commonly observed negative dependence for protein‒ligand interactions exhibiting extreme enthalpy‒entropy compensation, where the solvent contribution to the energetics reflects changes in the extent of ordered water structure in hydrophobic environments.

Gas hydrate inhibition by urea and its blends with vinyl lactam polymer: Paving the way to green hybrid inhibitors

Urea is an environmentally benign substance considered a promising gas hydrate inhibitor in flow assurance. Nevertheless, its effect on gas hydrate formation kinetics remains poorly understood. This study investigates the impact of urea and hybrid urea/polymer KHI samples on the nucleation and growth kinetics of sII natural gas hydrates. Hydrate formation was observed at a lower onset temperature with increasing urea and polymer concentration. The nucleation of sII hydrate in aqueous urea solutions occurred at a higher subcooling (7.50 ± 0.58 K at 30 mass%) than in pure water (5.17 ± 0.69 K). These findings indicate that urea acts as a nucleation inhibitor of sII hydrates, although its capacity is not as potent as that of polymer KHI.The analysis of the hydrate nucleation probability distributions revealed that the sII hydrate nucleation rate exhibited a significant decline, approximately one order of magnitude, at subcooling of 5.3–6 K for 20 mass% urea compared to water. A similar behavior was noticed in an aqueous solution of polymer KHI. Urea has succeeded in providing a total benefit of up to 10 K in hydrate onset temperature due to a shift in the hydrate stability zone and nucleation retardation.Consequently, urea is a green dual-acting anti-hydrate chemical that inhibits the formation of sII hydrates by thermodynamic and kinetic mechanisms. Besides, adding 10 mass% urea increases the cloud point temperature of vinyl lactam polymer Luvicap 55W by 14 K. Urea is an additive that considerably augments the stability of the polymer in aqueous solutions at elevated temperatures. These findings make urea an effective and environmentally friendly top-up inhibitor that significantly enhances the anti-hydrate properties of polymer KHI.

Modulating Interfacial Properties in Pseudoternary Microemulsions via Urea Addition: Impact of Cosurfactant on the Reverse Micellar Structure and Interactions.

We have studied the structural and interfacial properties of CTAB/isooctane/alcohol/aqueous urea reverse micelles (RMs) for the first time using time-resolved fluorescence and small-angle X-ray scattering techniques. The chain length of alcohol, used as cosurfactant, has been varied to design three microemulsion systems: CTAB/1-butanol, CTAB/1-hexanol, and CTAB/1-octanol/isooctane/water, at a fixed water loading ratio, w0 = 12. Time-resolved fluorescence anisotropy studies indicate that urea induces micellar aggregation in CTAB/1-butanol and CTAB/1-hexanol RMs but breaks down RM aggregates in CTAB/1-octanol RMs. Urea addition slows down solvation dynamics inside RMs at higher urea concentrations, evident from the longer lifetimes of solvent correlation decay. The underlying changes in microemulsion structure and intermicellar interactions are studied using small-angle X-ray scattering studies. The significant intermicellar interactions were modeled using the sticky hard sphere (SHS) for the CTAB/1-butanol and CTAB/1-hexanol RMs and by using the Macroion model for the CTAB/1-octanol RMs. The two different structural factors highlight the dominance of attractive and repulsive forces, respectively. Although there is no change in RM shape, the combination of urea addition and chain length variation in cosurfactants significantly alters the size and interface in these pseudoternary RMs.

Tin oxide nanoparticles-coated cathode for the detection of aqueous urea using compost-based microbial fuel cell configuration

Tin oxide nanoparticles-coated cathode for the detection of aqueous urea using compost-based microbial fuel cell configuration

Deep‐Ultraviolet Photoexcitation of Aqueous Urea Forms Carbamic Acid/Carbamate in Less Than One Picosecond

Deep‐Ultraviolet Photoexcitation of Aqueous Urea Forms Carbamic Acid/Carbamate in Less Than One Picosecond

Deep-Ultraviolet Photoexcitation of Aqueous Urea Forms Carbamic Acid/Carbamate in Less Than One Picosecond.

Urea is believed to have been essential to the synthesis of prebiotic nucleotides and thereby the RNA or DNA of the first lifeforms. Models suggesting that life began in wet-dry cycles around shallow aquatic ponds imply that reactants such as urea were exposed to deep ultraviolet irradiation from the young sun. Detrimental photodissociation of urea induced by deep UV excitation potentially challenges these models. We here follow the primary deep ultraviolet photochemistry of aqueous urea. The data show that urea is barely excited at 200 nm due to weak ultraviolet absorption. The likelihood of photodissociation is further reduced by strong intra-molecular coupling of the CN and CO stretch vibrations accompanied by an efficient dissipation of the excitation energy to the surrounding water molecules mitigated by urea-water hydrogen bonds. We find that 54±5 % of the excited urea molecules dissociate. Reactions between the photoproducts and surrounding solvent molecules form carbamic acid or the carbamate anions within 0.6 ps. The molecules that do not dissociate return to the electronic ground state in 2 ps. Interestingly, the photodissociation processes of urea in the aqueous phase is different from earlier reported reactions observed following the VUV photolysis of urea in noble gas matrices and highlight the potential influence of water on the prebiotic photochemistry.

Trimethylamine-N-oxide depletes urea in a peptide solvation shell

Trimethylamine-N-oxide (TMAO) and urea are metabolites that are used by some marine animals to maintain their cell volume in a saline environment. Urea is a well-known denaturant, and TMAO is a protective osmolyte that counteracts urea-induced protein denaturation. TMAO also has a general protein-protective effect, for example, it counters pressure-induced protein denaturation in deep-sea fish. These opposing effects on protein stability have been linked to the spatial relationship of TMAO, urea, and protein molecules. It is generally accepted that urea-induced denaturation proceeds through the accumulation of urea at the protein surface and their subsequent interaction. In contrast, it has been suggested that TMAO's protein-stabilizing effects stem from its exclusion from the protein surface, and its ability to deplete urea from protein surfaces; however, these spatial relationships are uncertain. We used neutron diffraction, coupled with structural refinement modeling, to study the spatial associations of TMAO and urea with the tripeptide derivative glycine-proline-glycinamide in aqueous urea, aqueous TMAO, and aqueous urea-TMAO (in the mole ratio 1:2 TMAO:urea). We found that TMAO depleted urea from the peptide's surface and that while TMAO was not excluded from the tripeptide's surface, strong atomic interactions between the peptide and TMAO were limited to hydrogen bond donating peptide groups. We found that the repartition of urea, by TMAO, was associated with preferential TMAO-urea bonding and enhanced urea-water hydrogen bonding, thereby anchoring urea in the bulk solution and depleting urea from the peptide surface.

Thermo‐responsive polymer to clean fouled forward osmosis membrane after wastewater treatment: Excellent flux recovery

AbstractThermally responsive polymers (TRPs) have gained significant attention in the past decade due to their unique phase transition behavior, those exhibiting changes in properties with temperature variations. In water, hydrophilic block copolymers form helical structures that can transform into hydrophobic globules above the lower critical solution temperature (LCST). Fouling is one of the limiting issues for the forward osmosis (FO) process in wastewater treatment. In this work, after the treatment of wastewater from the paper and pulp industries, foulants were removed from the surface of the commercial polyamide thin‐film composite membrane of the FO process using polyvinyl methyl ether (PVME), a TRP with an LCST of 35–37°C. PVME was mixed with different aqueous solutions to form cleaning solutions. Foulant cleaning experiments utilized a 1% PVME (w/v) solution in 300 mL of de‐ionized (DI) water, while 1 M NaCl solution served as the draw solution (DS) in the FO process. Comparing the water flux (J) and change in membrane hydraulic resistance (Rf) among pristine, fouled, and cleaned membranes revealed a 56.67% increase in water flux and a 51.68% decrease in membrane resistance after PVME mixed with DI water cleaning solution showcasing its effectiveness in improving membrane performance and reducing fouling. The cleaning efficiency of two solutions, that is, 1% PVME mixed in DI water and 1% PVME mixed in 1 M aqueous urea solution, is compared. Results showed that the former cleaning solution helped to obtain 32.62% higher water flux and 56.05% less membrane resistance. Various membrane characterizations are performed, such as field emission scanning electron microscopy (FE‐SEM), which characterizes the membrane's pore structure and surface morphology, while a contact angle analyzer assesses hydrophilicity. This research highlights the use of TRPs as effective cleaning agents, enhancing membrane performance by effectively removing foulants on the membrane surface. Investigating alternative cleaning solutions also provides insights for optimizing water treatment processes.Highlights Cleaning of fouled thin‐film composite membrane using thermal‐responsive polymers (TRPs). Polyvinyl methyl ether, a TRP with an lower critical solution temperature of 35–37°C used as a cleaning agent. 60% increase in water flux was observed after the single‐step cleaning process. Multiple uses of TRP for cleaning performed with no membrane damage.

Infrared Thermography Investigation of Crystallization in Acoustically Levitated Supersaturated Aqueous Solution

In this study, crystallization in highly supersaturated aqueous urea solutions was investigated using in situ infrared thermography facilitated by an acoustic levitation apparatus. A notable contribution of this thermographic approach is the identification of a transient heat release signature, particularly pronounced beyond the solubility limit, indicating the enhanced formation of bonds between urea molecules in the supersaturated states. Surprisingly, the temporal evolution of the heat release measurements on an acoustically levitated droplet strongly suggests a two-stage process for urea crystallization. A comprehensive statistical analysis based on classical nucleation theory is used to further investigate the exceptionally high degree of supersaturation and the emergence of prominent heat signatures observed toward the onset of crystallization.

Thermal properties of multi-layered seamed fabrics under wet state

PurposeIn experiments utilising sweat solution and distilled water, seamed ensembles performed less thermally efficiently than unseamed fabrics.Design/methodology/approachWater may not accurately reflect perspiration when testing multi-layered clothes for thermal comfort in wet state. Most researchers used water or sodium chloride (NaCl) to measure wet state thermal comfort. However, human perspiration is an extremely complex mixture of aqueous chemicals, including minerals, salts, lipids, urea and lactic acid. This study compares the effects of simulated sweat solution to distilled water on the thermal behaviour of a multi-layered fabric assembly with different seam patterns.FindingsExperiment results show that stitching decreases thermal resistance and thermal conductivity. Seam pattern of 10 cm diagonal spacing is more thermally resistant than 2.5 cm diagonal spacing. In comparison to that of simulated sweat, fabric that has been moistened with distilled water exhibits increased thermal conductivity. Hollow polyester wadding or micro polyester wadding as the intermediate layer exhibits greater thermal resistance than multi-layered construction with spacer fabric as middle layer.Originality/valueThis study considers human perspiration while designing protective clothing for wet thermal comfort.

Minimum conditions for accurate modeling of urea production via co-electrolysis

Co-electrolysis of carbon oxides and nitrogen oxides promise to simultaneously help restore the balance of the C and N cycles while producing valuable chemicals such as urea. However, co-electrolysis processes are still largely inefficient and numerous knowledge voids persist. Here, we provide a solid thermodynamic basis for modelling urea production via co-electrolysis. First, we determine the energetics of aqueous urea produced under electrochemical conditions based on experimental data, which enables an accurate assessment of equilibrium potentials and overpotentials. Next, we use density functional theory (DFT) calculations to model various co-electrolysis reactions producing urea. The calculated reaction free energies deviate significantly from experimental values for well-known GGA, meta-GGA and hybrid functionals. These deviations stem from errors in the DFT-calculated energies of molecular reactants and products. In particular, the error for urea is approximately -0.25 ± 0.10 eV. Finally, we show that all these errors introduce large inconsistencies in the calculated free-energy diagrams of urea production via co-electrolysis, such that gas-phase corrections are strongly advised.

Tough and On-Demand Detachable Wet Tissue Adhesive Hydrogel Made from Catechol Derivatives with a Long Aliphatic Side Chain.

Wet adhesion is critical in cases of wound closure, but it is usually deterred by the hydration layer on tissues. Inspired by dopamine-mediated underwater adhesion in mussel foot proteins, wet tissue adhesives containing catechol with 2-3 carbons side chains are reported mostly. To make wet adhesion of this type of adhesives much tougher, catechol derivatives with a long aliphatic side chain (≈10 atoms length) are synthesized. Then, a series of strong wet tissue adhesive hydrogels are prepared through photoinduced copolymerization of acrylic acid with synthetic monomers. The adhesive hydrogel has a high cohesion strength, that is, tensile strength and strain, and toughness of ≈1800kPa, ≈540%, and ≈4100kJm-3 , respectively. Its interfacial toughness on wet and underwater porcine skin is respectively ≈1300 and ≈1100 Jm-2 , and its adhesion strength to wet porcine skin is ≈153kPa. These values are much higher than those of dopamine-based adhesives in the same conditions, demonstrating that the long aliphatic side chain on catechol can greatly improve the wet tissue-adhesion. Additionally, the tough interfacial adhesion can be broken on demand with 5wt.% aqueous urea solution. This adhesive hydrogel is highly promising in safe wound closure.

Stabilizing α-Helicity of a Polypeptide in Aqueous Urea: Dipole Orientation or Hydrogen Bonding?

We propose a mechanism for α-helix folding of polyalanine in aqueous urea that reconciles experimental and simulation studies. Over 15 μs long, all-atom simulations reveal that, upon dehydrating the protein's first solvation shell, a delicate balance between localized urea-residue dipole interactions and hydrogen bonds dictates polypeptide solvation properties and structure. Our work clarifies the experimentally observed tendency of these alanine-rich systems to form secondary structures at low and intermediate urea concentrations. Moreover, it is consistent with the commonly accepted hydrogen-bond-induced helix unfolding, dominant at high urea concentrations. These results establish a structure-property relationship highlighting the importance of microscopic dipole-dipole orientations/interactions for the operational understanding of macroscopic protein solvation.

Bilayer Actuator Film for Urea Biosensing with Dual Responsiveness: Bending Actuation and Photonic Color Change.

A noninvasive sweat-based biosensor was developed for urea detection using a photonic bilayer actuator film (BAF) consisting of an interpenetrating polymer network (IPN) as the active layer and a flexible poly(ethylene terephthalate) (PET) substrate as the passive layer (IPN/PET). The active IPN layer comprises intertwined solid-state cholesteric liquid crystal and poly(acrylic acid) (PAA) networks. Urease was immobilized in the PAA network in the IPN layer of the photonic BAF. The interaction with aqueous urea altered the curvature and photonic color of the photonic urease-immobilized IPN/PET (IPNurease/PET) BAF. The curvature (and wavelength of the photonic color) of the IPNurease/PET BAF increased linearly with urea concentration (Curea) in the range of Curea = 20-65 (and 30-65) mM with a limit of detection value of 1.42 (and 1.34) mM. The developed photonic IPNurease/PET BAF exhibited high selectivity toward urea and excellent spike test results with real human sweat. This novel IPNurease/PET BAF is promising because it enables battery-free, cost-effective, and visual detection-based analysis without the use of sophisticated instruments. Furthermore, the application of this photonic IPN/PET BAF can be easily extended to other biosensors by immobilizing other receptors on the IPN.

Mechanistic Insights into Polyphenols' Aggregation Inhibition of α-Synuclein and Related Peptides.

While several polyphenols were found to either inhibit or modulate the aggregation of proteins implicated in neurodegenerative diseases, such as Parkinson's disease (PD), discrepant action mechanisms have been reported. This, in addition to some polyphenols' pan-assay interference compounds' reputation, casts some doubts concerning their therapeutic relevance. Here, we studied, through molecular dynamics and enhanced sampling methods, the aggregation of 11-mer peptides from the non-amyloid-β component, an aggregation-prone domain of α-synuclein (α-syn) implicated in PD and other synucleinopathies, in neat water and aqueous solutions of resveratrol (RSV) and gallic acid (GA). Further, simulations of the complete protein were carried out in aqueous urea, RSV, and GA solutions. Our results show that peptide aggregation is not disrupted by either phenolic compound. Thus, instead, intrusion of RSV and GA in the inter-peptide region induces a peptide-peptide re-orientation, favoring terminal interactions that manifest in the formation of barrierless solvent-separated configurations. Moreover, although the (poly)phenols induce a pronounced peptide dewetting at high concentrations, β-sheet-rich regions, a hallmark of α-syn aggregation, are not disrupted. Thus, our results indicate that, if anything, RSV and GA delay or modulate peptide aggregation at high concentrations via the stabilization of solvent-separated conformations as opposed to aggregation inhibition. Structural analysis of the full protein, however, shows that the (poly)phenols induce more extended conformations of α-syn, similar to urea, possibly also influencing its aggregation propensity. However, opposite to urea, the (poly)phenols reduce α-syn's conformational space, likely due to steric effects and a slowdown of the solvent dynamics. These effects are concentration-dependent and possibly unattainable at therapeutic-relevant concentrations. These results suggest that the aggregation inhibition activity of RSV and GA in vitro should involve, instead, either the non-covalent binding to oligomeric intermediates or the stabilization of the monomer and/or oligomers through the formation of covalent bonds of the respective quinones with α-syn. In addition, the enhanced aggregation tendency of the peptides observed here could be associated with the formation of non-toxic oligomers, reported for some polyphenols.

Corrosion of 1.4016 Ferritic Steel by Urea at High Temperature

The corrosion behavior of a ferritic unstabilized stainless steel 1.4016 during decomposition of aqueous urea solution at high temperature has been investigated. Corrosion was obtained from 100 h of cyclic heating (from room temperature up to 600 °C) and injection of aqueous urea solution on the steel plate in a laboratory-scale test bench. The evaluation procedure covered the metallographic analysis of corroded steel samples by high-resolution scanning electron microscopy (HR-SEM) and transmission electron microscopy (TEM). Uniform corrosion underneath deposits was found as one of the drivers for degradation of the steel. Damage happened by high-temperature depassivation of stainless steel due to the excess of the aggressive medium. Besides uniform corrosion, a nitridation layer underneath surface oxides together with chromium carbonitride particles precipitated through the whole depth of the sample was identified resulting in intergranular attack.

Preparation and Properties of a Novel Biodegradable Composite Hydrogel Derived from Gelatin/Chitosan and Polylactic Acid as Slow-Release N Fertilizer

To improve the efficient use of nitrogen and decrease the environmental pollution of N losses, a novel and biodegradable composite hydrogel was prepared by chemical cross-linking synthesis using gelatin (Gel), chitosan (CS) and polylactic acid (PLA) as raw materials. Urea as the nitrogen source was loaded into this new biodegradable hydrogel using the solution immersion method. The chemical structures of the composite hydrogels were characterized and their properties were analyzed by XRD and XPS. The regulation of urea loading and the swelling behavior of the composite hydrogel under different temperature conditions were investigated; the release behavior and release model of the composite hydrogel in the aqueous phase was explored. The results show that the loading of urea is controllable in aqueous urea solution with different concentrations. In the water phase, it shows a three-stage sustained release behavior, that is, the initial release rate of urea is relatively fast, and the medium release rate of urea gradually slows down, and finally the nutrient release rate tends to be flat. The release behavior in the water phase fits to the Ritger-Peppas model. Within 10 min, 180 min and 900 min, the cumulative nutrient release rate of gelatin/chitosan/PLA-urea (GCPU) composite hydrogel is 20%, 70% and 86%, respectively. Compared with pure urea, The urea diffusion time of GCPU was extended by 1350-times. In addition, the GCPU also has good water absorption and water retention properties, in which average water content can reach as high as 4448%. All of the results in this work showed that GCPU hydrogel had good water absorption and retention and N slow-release properties, which are expected to be widely used in sustainable agriculture and forestry, especially in arid and degraded land.

Interaction and physicochemical parameters of dodecyltrimethylammonium bromide and crystal violet dye mixture in aqueous alcohols and urea solution: Effects of change in composition and temperature

Herein, the interaction between dodecyltrimethylammonium bromide (DTAB), a cationic surfactant, and crystal violet (CV) has been studied by applying the conductometric method in aqueous solutions of short chain alcohols (ethanol, 1-propanol) and urea. The critical micelle concentration (CMC), counter ion binding (β) and the thermodynamics parameters (ΔGm0, ΔSm0 and ΔHm0) for the assembly of DTAB + CV system were determined. For the DTAB + CV micellization in presence of aqueous alcohols and urea solutions, a single break point was obtained in every circumstance. The values of CMC for the study system are found to upsurge with the increase of concentration of alcohols and urea as well as with the increase of temperature. The ΔGm0 values were found negative for DTAB + CV mixtures in the study media, which indicated that the micellization process was thermodynamically spontaneous. In all cases, the -ΔHm0 and -ΔSm0 values disclosed that the recommended interaction forces functioning amid DTAB and CV are the hydrophobic and electrostatic interactions.

Protein cysteine S-glycosylation: oxidative hydrolysis of protein S-glycosidic bonds in aqueous alkaline environments

Some glycoproteins contain carbohydrates S-linked to cysteine (Cys) residues. However, relatively few S-glycosylated proteins have been detected, due to the lack of an effective research methodology. This work outlines a general concept for the detection of S-glycosylation sites in proteins. The approach was verified by exploratory experiments on a model mixture of β-S-glucosylated polypeptides obtained by the chemical transformation of lysozyme P00698. The model underwent two processes: (1) oxidative hydrolysis of S-glycosidic bonds under alkaline conditions to expose the thiol group of Cys residues; (2) thiol S-alkylation leading to thiol S-adduct formation at the former S-glycosylation sites. Oxidative hydrolysis was conducted in aqueous urea, dimethyl sulfoxide, or trifluoroethanol, with silver nitrate as the reaction promoter, in the presence of triethylamine and/or pyridine. The concurrent formation of stable protein silver thiolates, gluconic acid, and silver nanoclusters was observed. The essential de-metalation of protein silver thiolates using dithiothreitol preceded the S-labeling of Cys residues with 4-vinyl pyridine or a fluorescent reagent. The S-labeled model was sequenced by tandem mass spectrometry to obtain data on the modifications and their distribution over the protein chains. This enabled the efficiency of both S-glycosidic bonds hydrolysis and S-glycosylation site labeling to be evaluated. Suggestions are also given for testing this novel strategy on real proteomic samples.

Анализ эффективности использования восстановителя оксидов азота отработавших газов дизелей

The relevance of the article is due to the need to radically improve the environmental performance of automobile diesels. The most significant gaseous toxic component of spent diesel engines are nitrogen oxides. The mechanisms and models of nitrogen oxides formation in the diesel combustion chamber are considered. The analysis of methods for reducing the emission of nitrogen oxides with diesel exhaust gases has been carried out. The most effective method of their purification from nitrogen oxides is the use of SCR technology, in which an aqueous urea solution is supplied to the diesel exhaust system. At a temperature of about 130 °C, urea decomposes into ammonia and carbon dioxide. Ammonia released from urea reacts with nitrogen oxides of exhaust gases, reducing them to nitrogen. A method for calculating the urea supply to the diesel exhaust system has been developed. Tests of the YAMZ-6566 diesel engine equipped with the SCR system were carried out. With an excess urea ratio of 1.03, the efficiency of the SCR system ranged from 89 to 100 %, depending on the operating mode of the diesel engine.