Stable Covalent Organic Frameworks Research Articles

Stabilizing atomic Ru species in conjugated sp2 carbon-linked covalent organic framework for acidic water oxidation

Suppressing the kinetically favorable lattice oxygen oxidation mechanism pathway and triggering the adsorbate evolution mechanism pathway at the expense of activity are the state-of-the-art strategies for Ru-based electrocatalysts toward acidic water oxidation. Herein, atomically dispersed Ru species are anchored into an acidic stable vinyl-linked 2D covalent organic framework with unique crossed π-conjugation, termed as COF-205-Ru. The crossed π-conjugated structure of COF-205-Ru not only suppresses the dissolution of Ru through strong Ru-N motifs, but also reduces the oxidation state of Ru by multiple π-conjugations, thereby activating the oxygen coordinated to Ru and stabilizing the oxygen vacancies during oxygen evolution process. Experimental results including X-ray absorption spectroscopy, in situ Raman spectroscopy, in situ powder X-ray diffraction patterns, and theoretical calculations unveil the activated oxygen with elevated energy level of O 2p band, decreased oxygen vacancy formation energy, promoted electrochemical stability, and significantly reduced energy barrier of potential determining step for acidic water oxidation. Consequently, the obtained COF-205-Ru displays a high mass activity with 2659.3 A g−1, which is 32-fold higher than the commercial RuO2, and retains long-term durability of over 280 h. This work provides a strategy to simultaneously promote the stability and activity of Ru-based catalysts for acidic water oxidation.

Robust Amide-Linked Fluorinated Covalent Organic Framework for Long-Term Oxygen Reduction Reaction Electrocatalysis.

The high energy demand of the evolving world opens the door to develop more sustainable and environmentally friendly energy sources. Oxygen reduction reaction (ORR) is a promising candidate, being the 2e- pathway of great interest for the green production of hydrogen peroxide. Metal-free covalent organic frameworks (COFs) electrocatalysts present a suitable alternative to substitute the noble-metals more commonly employed in this application. However, the lability of the linkages building up the framework raises an issue for their long-term use and application in aggressive media. Herein, a stable amide-linked COF is reported through post-synthetic modification of a previously reported imine-linked COF proven to be effective as an electrocatalyst, enhancing its chemical stability and electrochemical response. It is found that after the linkage transformation, the new electrocatalyst displays a higher selectivity toward the H2O2 production (98.5%) and an enhanced turnover frequency of 0.155s-1, which is among the bests reported to date for metal-free and COF based electrocatalysts. The results represent a promising step forward for metal-free non pyrolyzed electrocatalysts, improving their properties through post-synthetic linkage modification for long-term operation.

Ratiometric electrochemical biosensor based on Cu(II) modified covalent organic framework for the ultra-sensitive and specific detection of glutathione

As a vital biological polypeptide molecule, glutathione (GSH) is involved in the regulation of various life activities. Accurate and sensitive detection of GSH in human body is of great significance for the preliminary diagnosis of related diseases. In this research, Cu(II) modified TADH COF, which has been prepared by Cu2+ post-synthesis modification of the COF obtained through a condensation reaction of 1,3,5-(4-aminophenyl) benzene (TAPB) and 2,5-dihydroxy-1,4-benzenedicarboxaldehyde (DHTP), and methylene blue (MB) molecules are combined to construct a ratiometric electrochemical sensor for achieving specific and ultra-sensitive detection of GSH. As a stable and active covalent organic framework material, TADH COF possesses the special O(–OH) and N(CN) binding sites, which can load and coordinate with Cu2+ effectively. The obtained Cu(II)-TADH COF serves as a sensitive electrode material for sensing GSH due to “extrusion effect” caused CuCl solid-state electrochemical signal degeneration by the specific binding of Cu and GSH while MB provides a stable electrical signal in the electrochemical sensing process as an internal reference for eliminating errors and making the detection results more accurate. The constructed electrochemical sensing platform Cu(II)-TADH COF/MB/GCE exhibited an ultrahigh sensitivity with a limit of detection (LOD) of 0.0093 nM (S/N = 3), wide linear range of 0.05 nM–40 μM and high accuracy. For the detection of GSH in real samples including human blood, serum and urine samples, the sensor also showed excellent sensing performance. This is the first research on ratiometric electrochemical sensing platform for the ultra-sensitive detection of glutathione based on covalent organic frameworks, which provides an original and novel strategy for the electrochemical detection of GSH with COF materials.

Stable and highly efficient extraction of U(VI) from seawater by covalent organic frameworks and amidoxime co-functionalized MXene

Seawater is rich in uranium resources, but the marine environment is complicated and changeable, as well as the presence of a lot of competing ions. These are disturbing factors that cannot be ignored in seawater uranium extraction. The synthesis of adsorbents with good stability, high selectivity and large adsorption capacity has been the focus of attention. The composite adsorbent MXene-AO@LZU1 was prepared using electrostatic self-assembly of transition metal carbides and nitrides (MXenes) with structurally stable covalent organic frameworks (COF-LZU1). The results of characterizations showed that MXene-AO@LZU1 was rich in functional groups and had an effective improvement in specific surface area. MXene-AO@LZU1 exhibited an efficient performance for [UO2(CO3)3]4- with an adsorption saturation capacity of 88.8 mg·g−1. The adsorption amount in the simulated seawater also reached 6.8 mg·g−1. MXene-AO@LZU1 had a good selectivity for uranium and outstanding stability under various extreme conditions. In addition, XPS showed that the adsorption of uranium by MXene-AO@LZU1 relied mainly on the complexation of oxygen/nitrogen-containing functional groups with [UO2(CO3)3]4-. This study explored the great potential of MXenes and COFs in seawater uranium extraction, indicating that MXene-AO@LZU1 was an efficient and stable adsorbent with good development prospects. This finding was of great importance for the application of composite materials in actual environmental cleanup, and could be extended to efficiently remove other pollutants by rational ligands design.

Boosting Aluminum Storage in Highly Stable Covalent Organic Frameworks with Abundant Accessible Carbonyl Groups

AbstractAluminum batteries employing organic electrode materials present an appealing avenue for sustainable and large‐scale energy storage. Nevertheless, conventional organic materials encounter limitations due to their restricted active sites, known instability, and sluggish redox kinetics. In this study, a redox‐active covalent organic framework supported by CNT is reported, enriched with substantial C═O groups, as an advanced cathode material for Al‐organic batteries. Theoretical simulation and ex situ analysis unveil the pivotal roles of C═O groups in effectively storing AlCl2+. As a result, Al batteries with the organic cathode exhibit a specific capacity of 290 mAh g−1 at 0.2 A g−1 and outstanding rate performance. Furthermore, it retains a reversible capacity of 170 mAh g−1 even after 32 000 cycles at 10 A g−1 and attains an energy density of 389 Wh kg−1. The remarkable performance stems not only from the abundant C═O and C─N groups enabling the storage of multiple AlCl2+ by the favorable pseudocapacitive process, but also from the synergistic interplay between the robust COF network and the conductive CNT channels that significantly enhances structural stability and accelerates ion/electron diffusion. This work stands to inspire further research in the pursuit of stable organic cathodes, fostering designs with plentiful accessible redox‐active sites to boost energy storage capabilities.

Superprotonic conductivity of ketoenamine covalent-organic frameworks grafted by imidazole-based units

The achievement of covalent organic frameworks (COFs) with high stability and exceptional proton conductivity is of tremendous practical importance and challenge. Given this, we hope to prepare the highly stable COFs carrying CN connectors and enhance their proton conductivity via a post-modification approach. Herein, one COF, TpTta, was successfully synthesized by employing 1,3,5-triformylphloroglucinol (Tp) and 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)-trianiline (Tta) as starting materials, which has a β-ketoenamine structure bearing a large amount of –NH groups and intramolecular H-bonds. TpTta was then post-modified by inserting imidazole (Im) and histamine (His) molecules, yielding the corresponding COFs, Im@TpTta and His@TpTta, respectively. As a result, their proton conductivities were surveyed under changeable temperatures (30–100 °C) and relative humidities (68–98 %), revealing a degree of temperature and humidity dependence. Impressively, under identical conditions, the optimum proton conductivities of the two post-modified COFs are 1.14 × 10−2 (Im@TpTta) and 3.45 × 10−3 S/cm (His@TpTta), which are significantly greater than that of the pristine COF, TpTta (2.57 × 10−5 S/cm). Finally, their proton conduction mechanisms were hypothesized based on the computed activation energy values, water vapor adsorption values, and structural properties of these COFs. Additionally, the excellent electrochemical stability of the produced COFs was expressed, as well as the prospective application value.

Construction of covalent organic frameworks membranes in situ through nonsolvent-induce phase separation for fast and accurate nanofiltration

With the development of covalent organic frameworks (COFs), their superior separation performance in membrane separation has gradually becoming apparent. The method of combining COFs with membrane materials is crucial for their applications prospect. In this study, inspired by the traditional Chinese mortise and tenon structure, we selected 1,3,5-triacetaldehyde mesityl phenol (TFP) and 1,3,5-tris(4-aminophenyl)benzene (TAPB) as the reactive building monomers. P-Phenylenediamine (PDA) was introduced into the casting solution to construct Polyether-sulfone (PES) bottom membranes with amino ligand sites, utilizing the phase transition effect generated by the non-invasive solvent-induced method (NIPS). Subsequently, COFs composite nanofiltration membranes with two-dimensional layered structures were prepared through mild interfacial polymerization (IP) under optimized reaction conditions. The synthesis of COFs composite nanofiltration membranes was demonstrated through a series of characterizations, including scanning transmission electron microscopy and infrared spectroscopy. The COFs composite nanofiltration membranes synthesized by this method exhibited better alignment, greater chemical stability, and higher separation efficiency compared to traditional interracially polymerized COFs composite nanofiltration membranes. As the method involves the addition of additives, it can be more widely applied to a broad range of organic polymer membranes. Furthermore, we demonstrated the effectiveness of the COF composite nanofiltration membranes produced using this method in the separation of molecular dyes. They exhibited rejection exceeding 99% for 0.1 g L−1 methyl blue (MB), Congo red (CR) and chrome black-T (EBT). Additionally, they achieved separation fluxes of up to 300 L m−2 h−1 bar−1 for mixed solutions (dyes/salts) and proved to be effective under extreme conditions, such as 1 M HCl/NaOH. Moreover, COFs-NH2PES composite nanofiltration membranes exhibited the ability to efficiently separate dye molecules of different sizes. This work introduces new ideas for constructing stable and durable COF functional composite membrane materials for practical applications.

Synergistically regulating Zn-ion flux and accelerating ion transport kinetics via zincophilic covalent organic framework interlayer for stable Zn metal anode

Zn metal is considered as an ideal anode for aqueous zinc-ion batteries (AZIBs) owing to the inherent merits of low cost, high theoretical capacity, and remarkable safety. However, the formation of Zn dendrites and water-induced parasitic reactions hamper the commercialization of AZIBs. Herein, a synergetic strategy to accelerate ion transfer kinetics and regulate Zn-ion flux has been proposed to achieve dendrite-free Zn anodes via a series of zincophilic covalent organic framework (COF) films. The nanoporous and mechanically stable COF films synthesized by the liquid–liquid interfacial polymerization can be straightforward transferred on the Zn foil surface through a dip-coating technique. Benefiting from the affinity between Zn2+ and electron-rich ketone, the zincophilic COF interlayers promote the de-solvation of hydrated Zn2+, simultaneously offer ample Zn2+ transport channels to facilitate rapid diffusion and regulating a homogenous Zn2+ flux, thereby inhibiting the dendritic growth and leading to the uniform Zn deposition. Additionally, the COF films with strong adherence and large surface area effectively separate Zn anodes from bulk aqueous electrolytes, inhibiting the water-induced corrosion reactions. As a result, the symmetric cell with COF-modified Zn anode exhibited a stable cycling lifetime more than 900 h at 1 mA∙cm−2 and 1 mAh∙cm−2, accompanied by a low voltage polarization of merely 74.3 mV. As a simple approach to synergistically restrict Zn-ion flux and enhance ion transport kinetics using zincophilic COF films via interfacial synthesis, this work would provide new insights into developing highly stable Zn anodes.

Irreversible bonds for higher stability of COF materials in photocatalytic reactions

Covalent organic frameworks (COFs), one of a multitude of advanced mainstream materials in photocatalysts, are crystalline porous materials with tunable topology and high porosity and are connected by dynamic covalent bonds. We sought to achieve efficient photocatalytic yields, making the stability of the bond energy crucial. Stable bond energy will enable our products to be more economically efficient. At present, the main photocatalysts are reversible imine bonds and other 2D COFs, but irreversibly stable COFs are seldom involved. Therefore, this review surveys the relevant literature to explore the stability of irreversible bond energy, elaborating the synthesis schemes of irreversible bonds. Irreversibly connected bonds will improve the stability and durability of our synthesized catalyst in practical applications, so we seek to explore the stability of bond energy for our practical applications. In this review, we offer a detailed summary of the irreversible bonding pattern, explore the stability of COFs, and summarize classic highly crystalline ordered semiconductor COFs with irreversible bonding methods.

Lithiophilic Covalent Organic Framework as Anode Coating for High-Performance Lithium Metal Batteries.

The growth of disorganized lithium dendrites and weak solid electrolyte interphase greatly impede the practical application of lithium metal batteries. Herein, we designed and synthesized a new kind of stable polyimide covalent organic frameworks (COFs), which have a high density of well-aligned lithiophilic quinoxaline and phthalimide units anchored within the uniform one-dimensional channels. The COFs can serve as an artificial solid electrolyte interphase on lithium metal anode, effectively guiding the uniform deposition of lithium ions and inhibiting the growth of lithium dendrites. The unsymmetrical Li||COF-Cu battery exhibits a Coulombic efficiency of 99 % at a current density of 0.5 mA cm-2 , which can be well retained up to 400 cycles. Meanwhile, the Li-COF||LFP full cell shows a Coulombic efficiency over 99 % at a charge of 0.3 C. And its capacity can be well maintained up to 91 % even after 150 cycles. Therefore, the significant electrochemical cycling stability illustrates the feasibility of employing COFs in solving the disordered deposition of lithium ions in lithium metal batteries.

Lithiophilic Covalent Organic Framework as Anode Coating for High‐Performance Lithium Metal Batteries

AbstractThe growth of disorganized lithium dendrites and weak solid electrolyte interphase greatly impede the practical application of lithium metal batteries. Herein, we designed and synthesized a new kind of stable polyimide covalent organic frameworks (COFs), which have a high density of well‐aligned lithiophilic quinoxaline and phthalimide units anchored within the uniform one‐dimensional channels. The COFs can serve as an artificial solid electrolyte interphase on lithium metal anode, effectively guiding the uniform deposition of lithium ions and inhibiting the growth of lithium dendrites. The unsymmetrical Li||COF−Cu battery exhibits a Coulombic efficiency of 99 % at a current density of 0.5 mA cm−2, which can be well retained up to 400 cycles. Meanwhile, the Li‐COF||LFP full cell shows a Coulombic efficiency over 99 % at a charge of 0.3 C. And its capacity can be well maintained up to 91 % even after 150 cycles. Therefore, the significant electrochemical cycling stability illustrates the feasibility of employing COFs in solving the disordered deposition of lithium ions in lithium metal batteries.

Carboxyl-functionalized magnetic amide-linked covalent organic framework for efficient extraction of multi-class mycotoxins from soybeans prior to HPLC-MS/MS analysis

Mycotoxins co-contamination in soybean poses great risks to human health, however, due to their diverse structures, it is difficult to simultaneously extract and detect these multi-mycotoxins. By incorporating modification of hydrophilic carboxyl groups with the hydrophobic properties of covalent organic frameworks, a stable cubic carboxyl-functionalized magnetic amide-linked covalent organic framework were fabricated, characterized and utilized as adsorbents for magnetic solid phase extraction (MSPE) of eleven frequently detected mycotoxins from soybeans followed by HPLC-MS/MS analysis. The key MSPE parameters were screened using the Plackett-Burman design and optimized with the Box-Behnken design for response surface methodologies. Under the optimal experimental conditions, the linear range was 0.2–50 μg/kg, the limits of detection were 0.1–1.4 μg/kg. The established method was applied for the soybean analysis with satisfactory recoveries (70.8–108.3%) and precision (intra- and inter-relative standard deviations of 2.1–9.2% and 1.6–11.1%, respectively). With proper modification, this method may have great application potential for simultaneously analyzing and monitoring the multi-mycotoxin contamination in foods to ensure consumer safety and public health.

Regenerable and Highly Stable Two-Dimensional Imine-Based Covalent Organic Framework for Simultaneous Rapid Detection and Adsorption of Cu2+ Ions.

The development of efficient fluorescent probes and adsorbents for detecting and removing Cu2+, which pose potential environmental and health risks, is a highly active area of research. However, achieving simultaneously improved fluorescence detection efficiency and enhanced adsorption capacity in a single porous probe remains a significant challenge. In this study, we successfully synthesized a two-dimensional imine-based TAP-COF using 2,4,6-triformylphloroglucinol and tri(4-aminophenyl)amine as raw materials. TAP-COF exhibited excellent properties, including a large specific surface area of 685.65 m2·g-1, exceptional thermal stability (>440 °C), chemical stability, temporal stability, and recyclability. Fluorescence testing revealed that TAP-COF exhibited remarkable specificity and high sensitivity for detecting Cu2+. The fluorescence mechanism, in which the excited state intramolecular proton transfer was impeded by the interaction of Cu2+ with C═O and C-N bonds on TAP-COF upon the addition of Cu2+, was further elucidated through experimental and theoretical methods. Furthermore, the adsorption capacity of TAP-COF toward Cu2+ was investigated, confirming the excellence of TAP-COF as a fluorescent probe and adsorbent for the specific detection and removal of Cu2+. This work holds significant implications for improving environmental and human health concerns associated with Cu2+ contamination.

Nitrogen-rich covalent organic framework as a practical coating for effective determinations of polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are high-profile organic pollutants to be poisonous, carcinogenic, and mutagenic, and widely distributed at trace levels in the environment. In order to effectively enrich PAHs, two stable covalent organic frameworks (COFs, TAPT-OMe-PDA and TPB-DMTP) were prepared by combining 2,4,6-tri(4-aminophenyl)-1,3,5-triazine (TAPT) and 1,3,5-tri(4-aminophenyl) benzene (TAPB) with 2,5-dimethoxy-phenyl-1,4-diformaldehyde (OMe-PDA), respectively. Even though the surface area of TAPT-OMe-PDA was much lower than that of TPB-DMTP, it still demonstrated much better extraction efficiencies towards PAHs as the solid phase microextraction (SPME) coating. Therefore, the TAPT-OMe-PDA coated fiber was coupled with gas chromatography-mass spectrometry (GC-MS) to establish a practical and sensitive method, after the extraction parameters (extraction time, extraction temperature, desorption temperature, desorption time, salt concentration and pH) were optimized. This developed analytical method showed wide linear ranges, low limits of detection, good repeatability and reproducibility. Finally, five PAHs in three water samples were detected and quantified precisely (2.72–38.7 ng·L-1) with satisfactory recoveries (88.3%–118%).

Enhancing ionic conductivity and suppressing Li dendrite formation in lithium batteries using a vinylene-linked covalent organic framework solid polymer electrolyte

A novel solid polymer electrolyte based on chemically stable vinylene-linked covalent organic framework was developed, demonstrating enhanced Li+ conductivity and improved battery performance.

Rapid and in-situ preparation COFs coated capillary by adsorption method for the separation and determination of phthalate ester using CEC

As a novel class of stationary phase materials, covalent organic frameworks (COFs) have shown great promise in open-tubular capillary electrochromatography. However, the current preparation of COFs coating capillaries heavily relies on tedious and time-consuming covalent bond methods. In this work, a novel, simple and rapid adsorption method was developed for fabrication of TPB-DMTP COF (fabricated from 1,3,5-tris(4-aminophenyl)benzene (TPB) and 2,5-dimethoxyterephthalaldehyde (DMTP)) coated capillary. Due to the crystallization process of the COF is greatly shortened because pre-modification capillary does not require silane coupling agent, this method enables the rapid preparation of COFs-coated capillaries. The organic molecular building units only need 25 min to form a stable COFs coating on the inner wall of a capillary by this method. To our knowledge, this is the shortest method for preparing COFs coated capillary up to now. The performance of the TPB-DMTP COF coated capillary was evaluated by using phthalate esters as model analytes. The results demonstrated that the TPB-DMTP COF coated capillary has excellent repeatability and stability. The relative standard deviations (RSDs) of the analyte's retention time of intra-day, inter-day and column-to-column were in the range of 0.05 %–0.27 %, 0.31 %–0.63 % and 0.31 %–0.88 %, respectively. And, no significant changes were observed in separation efficiency and retention time after over 200 runs. Finally, the TPB-DMTP COF coated capillary was applied for the determination of phthalates in marketed plastic bag and the recovery ranged from 88.0 % to 114.0 %.

Design of stable covalent organic frameworks for transport regulation of mass and energy

Design of stable covalent organic frameworks for transport regulation of mass and energy

Stable light-emitting bionic antibody-conjugated covalent organic frameworks for the adsorption of urea and control of ethyl carbamate

In this paper, a novel azide-modified covalent organic framework conjugated bionic antibody microspheres (COFs(azide)@BAs) were prepared for the adsorption of urea and indirect control of ethyl carbamate (EC) in the processing of Huangjiu. To improve the fluorescence properties and specific binding ability to target, COFs(azides) were synthesized using post-modification of copper-catalyzed azide-alkyne cycloaddition (CuAAC). The aggregation-induced enhancement (AIE) interaction between COFs(azides)@BAs and urea induced an enhanced fluorescence behavior. The detection limit of urea was as low as 13 ng L−1 (R2 = 0.9896) in the linear range of 0.05–5 μg L−1. In addition, a satisfactory control rate for the removal of EC was achieved by COFs(azide)@BAs in the simulated system of Huangjiu processing. Therefore, this research broadened the path for the application of optical sensing systems in food safety control, which had important food safety implication and great economic value.

Synthesis of stable and efficient amide-based covalent organic frameworks fiber coatings for the improved solid-phase microextraction of polar aromatic amines

BackgroundDeveloping facile and general functionalization strategies to improve the durability of covalent organic framework (COF) coatings and their affinity for polar targets is of great significance for solid-phase microextraction (SPME) technology. ResultsIn this work, a facile and general amidation strategy was developed for conversion from reversible (imine) to irreversible (amide) linkages in COF coatings. After the amidation, the durability of the obtained amide-linked covalent organic framework (Am-P-COF) coating was greatly improved, and the adsorption efficiency for polar aromatic amines (AAs) was also significantly increased. Moreover, this strategy is also applicable to the amidation of other two COF coatings, showing good general applicability. The obtained Am-P-COF coated fiber was used for SPME, and then coupled with gas chromatography tandem mass spectrometry (GC-MS/MS) to detect AAs. Under the optimal SPME conditions (extraction temperature: 50 °C, extraction time: 30 min, stirring rate: 600 rpm, pH: 8, NaCl concentration: 5.0 mg mL−1, desorption temperature: 290 °C and desorption time: 10 min), a detection method for trace AAs was established. The established method possess wide linear ranges (0.5–500.0 ng L−1), good correlation coefficients (0.9986–0.9993) and low detection limits (0.1–0.5 ng L−1). Moreover, the established method had also been successfully applied to detection of trace AAs in bottled tea beverage and plastic bags packed tea with satisfactory recoveries (83.5 %–116.8 %). Significance and noveltyThis research provides a facile and general pathway for increasing the durability of COF coatings and affinity to the polar AAs. The detection method based on the obtained fibers possesses high sensitivity, satisfactory reproducibility and good precision.

Robust covalent organic frameworks membranes for ultrafast dye/salt separation in harsh environments

Although covalent organic frameworks (COFs) membranes have promising applications in water treatment due to their ordered structure and adjustable pore size, most of them are imine-linked ones, which severely limits their application in harsh environments. Herein, we offer a stable novel COFs membrane which is composed of hydrazone bonds and β-ketoenamine structures. Such β-ketoenamine based COFs composite membrane was fabricated via interfacial catalytic polymerization on a nylon substrate, which was generated at the water (P-Toluenesulfonic acid)/n-hexane (2,5-dimethoxyterephthalhydrazide, 1,3,5-triformylphoroglucinol) interface. The resultant COFs membrane demonstrates excellent chemical stability in strong acidic (2 mol/L)/alkaline (9 mol/L)/organic solvents (dioxane, acetone, methanol, and ethanol) media. The optimized COFs membrane achieved 109.73 L m−2 h−1 bar−1 permeance in Congo Red aqueous solution and 99.56 % CR rejection. This study exploits a novel approach to produce robust COFs membranes under extreme conditions.