Chemical Warfare Agent Simulants Research Articles

A Long Wave-Infrared Miniatured Quantum Dot Spectrometer.

In this work, a long-wave infrared (LWIR) quantum dot (QD) spectrometer was constructed for the first time by integrating a 255-element HgSe QD filter array with an LWIR array detector. The filter array was fabricated using a combination inkjet printing strategy with eight types of T-dodecyl mercaptan-terminated HgSe QD inks. The stability and morphology of the QDs were improved by optimizing the purification methodology and ligand modification. Combined with the compressive-sensing-based least-squares linear regression (CS-LS) algorithm, the LWIR QD spectrometer achieved a spectral resolution of 5.4 cm-1 over a wide spectral range of 8 to 14 μm, enabling the detection of the chemical warfare agent simulant dimethyl methylphosphonate. This technology is expected to facilitate the development of smaller volumes and more accurate identification of various targets in the future. This paper offers an approach to fabricating low-cost LWIR spectrometers and promoting the scale-up applications of QD devices.

Effect of wavelength and liquid on formation of Ag, Au, Ag/Au nanoparticles via picosecond laser ablation and SERS-based detection of DMMP.

The present study investigates the effects of input wavelength (1064, 532, and 355 nm) and surrounding liquid environment (distilled water and aqueous NaCl solution) on the picosecond laser ablation on silver (Ag), gold (Au), and Ag/Au alloy targets. The efficacy of the laser ablation technique was meticulously evaluated by analyzing the ablation rates, surface plasmon resonance peak positions, and particle size distributions of the obtained colloids. The nanoparticles (NPs) were characterized using the techniques of UV-visible absorption, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Furthermore, NPs of various sizes ranging from 6 to 35 nm were loaded onto a filter paper by a simple and effective drop-casting approach to achieve flexible surface-enhanced Raman spectroscopy (SERS) substrates/sensors. These substrates were tested using a simple, portable Raman device to identify various hazardous chemicals (malachite green, methyl salicylate, and thiram). The stability of the substrates was also systematically investigated by determining the decay percentages in the SERS signals over 60 days. The optimized SERS substrate was subsequently employed to detect chemical warfare agent (CWA) simulants such as methyl salicylate (a CWA simulant for sulfur mustard) and dimethyl methyl phosphonate (has some structural similarities to the G-series nerve agents) at different laser excitations (325, 532, and 633 nm). A notably higher SERS efficiency for CWA simulants was observed at a 325 nm Raman excitation. Our findings reveal that a higher ablation yield was observed at IR irradiation than those obtained at the other wavelengths. A size decrease of the NPs was noticed by changing the liquid environment to an electrolyte. These findings have significant implications for developing more efficient and stable SERS substrates for chemical detection applications.

Low-Temperature Decomposition and Oxidation of the Nerve Agent Simulant on Mesoporous Nickel Oxide and Cu-Doped Nickel Oxide.

In an effort to develop the next frontier filtration material for chemical warfare agent (CWA) decomposition, we synthesized mesoporous NiO and CuxNi1-xO (x = 0.10 and 0.20) and studied the decomposition of CWA simulant diisopropyl fluorophosphate (DIFP) on their surfaces. Mesoporous NiO and CuxNi1-xO were fully characterized and found to be a solid solution with no phase separation up to 20% copper dopant. The synthesized materials were successfully templated producing ordered mesoporous metal oxides with high surface areas (67.89- 94.38 m2/g). Through Raman spectroscopy, we showed that pure NiO contained a high concentration of Ni2+ vacancies, while Cu2+ reduced these defects. Through in situ infrared spectroscopy, we determined the surface species formed, potential pathways, and driving factors for decomposition. Upon exposure of DIFP, all materials produced similar decomposition products CO, CO2, carbonyls, and carbonates. However, decomposition reactions were sustained longer on mesoporous NiO, facilitated by the higher Ni2+ vacancy concentration. NiO was further studied with DIFP, first at low dosing temperatures (-50 °C), which still resulted in the production of CO and carbonates, and then, second, with a higher pretreatment temperature, which showed the importance of terminal hydroxyls/water to fully oxidize decomposition products to CO2. Mesoporous NiO demonstrated high decomposition and oxidation capabilities at temperatures below room temperature, all without any external excitation or noble metals, making it a promising frontier filtration material for CWA decomposition.

The Application of Commercial Surface Acoustic Wave Radio Communication Filters as Transducers for DMMP Sensors.

In the present study, we used two popular radio communication SAW resonators as a base for gas sensors and tested their performance. Taking into account issues related to sensor sensitivity, the possibility of applying a sensor layer, the availability of devices, and other related issues, we selected two popular single-port resonators with center frequencies of 315 and 433 MHz (models R315 and R433, respectively) for testing purposes. Both resonators were equipped with a sensitive film of hexafluoroisopropanol-substituted polydimethylsiloxane, a material that selectively absorbs molecules with a high ability to form basic hydrogen bonds. Fabricated sensors were used to detect trace amounts of dimethyl methylphosphonate (DMMP) vapor, which has often been used in similar studies as a nerve chemical warfare agent simulant. Sensors using both devices loaded with sensor layers of an optimal thickness rapidly reacted to a gas containing DMMP at a concentration of 3 mg/m3, generating a stable analytical signal ranging from several to several dozen kilohertz. In the case of R433, the frequency signal was 20.5 kHz at 1 min from the beginning of exposure to DMMP. The obtained results showed that the used transducers exhibited good performance as a base for gas sensors. Finally, their suitability for sensing applications was confirmed by a comparison with the results obtained in previous similar studies.

Post‐Synthetic Modification of Mixed‐Metal UiO‐66 Framework for Rapid Neutralization of Chemical Warfare Agent Simulants

AbstractMetal‐organic frameworks (MOFs) are a promising class of materials for catalysis, offering unique opportunities for designing efficient and selective catalysts. In this study, we have focused on the synthesis and catalytic activity of a novel mixed metal MOF, Ce/Zr−UiO‐66@LiOtBu, designed for the rapid hydrolysis of chemical warfare agents simulants: dimethyl 4‐nitrophenyl phosphate (DMNP) and 2‐chloroethyl ethyl sulfide (CEES). This MOF was thoroughly characterized using powder X‐ray diffraction (PXRD), BET surface area, and inductively coupled plasma optical emission spectrometry (ICP‐OES). The catalytic performance of Ce/Zr−UiO‐66@LiOtBu was monitored in the hydrolysis of DMNP and CEES by using 31P NMR and GC‐MS respectively. Remarkably, the MOF demonstrated rapid and efficient catalytic activity, breaking the P−O bond in DMNP with 2 min and the hydrolysis of CEES was observed in less than 45 min The results suggest the potential application of Ce/Zr−UiO‐66@LiOtBu as a robust catalyst in the detoxification of chemical warfare agent simulants. Our findings highlight the novelty of Ce/Zr−UiO‐66@LiOtBu as a catalytically active MOF, showcasing the successful integration of cerium ions and lithium tert‐butoxide to enhance basicity.

UV-Cured Highly Crosslinked Polyurethane Acrylate to Serve as a Barrier against Chemical Warfare Agent Simulants.

Ultraviolet (UV) curing is an efficient and environmentally friendly curing method. In this paper, UV-cured polyurethane acrylates (PUAs) were investigated as potential military coatings to serve as barriers against chemical warfare agents (CWAs). Seven UV-cured PUA coatings were formulated utilizing hydroxyethyl methacrylate-capped hexamethylene diisocyanate trimer (HEMA-Htri) and trimethylolpropane triacrylate-capped polycarbonate prepolymer (PETA-PCDL) as the PUA monomers. Isobornyl acrylate (IBOA) and triethyleneglycol divinyl ether (DVE-3) were employed as reactive diluents. Gas chromatography was utilized to investigate the constitutive relationships between the structures of the PUA coatings and their protective properties against simulant agents for CWAs, including dimethyl methylphosphonate (DMMP), a nerve agent simulant, and 2-chloroethyl ethyl sulfide (CEES), a mustard simulant. The glass transition temperature (Tg) and crosslinking density (υe) of PUAs were found to be crucial factors affecting their ability to serve as barriers against CWAs. The incorporation of IBOA units led to enhanced Tg and barrier performance of the PUAs, resulting in a DMMP retention of less than 0.5% and nearly 0 retention of CEES. However, an excessive introduction of polycarbonate chains decreased the υe and barrier performance of the PUAs. These findings may offer valuable insights for enhancing the protection of UV-cured PU coatings against CWAs.

High performance methyl salicylate gas sensor based on noble metal (Au, Pt) decorated WO3 nanofibers

Methyl salicylate (MeSa) is known as a volatile plant pathogen biomarker and a chemical warfare agent simulant. Herein, high performance MeSa gas sensors were developed by optimizing morphology and composition of noble metal decorated tungsten trioxide (WO3) nanofibers. Using optimized nanofibers, 100 ppb of MeSa were readily sensed in dry air whereas the calculated low limit of detection (LLOD) is expected to be in a few tens of ppb. Pt-WO3 (1.1 at% Pt) nanofibers also show an excellent selectivity over other volatile organic compounds including aromatic compounds (i.e., benzene, toluene, ethyl benzene, p-xylene). Systematic characterization of sensors in environments with different oxygen contents indicated that surface carrier concentration significantly altered as a function of Au and Pt content. Although 1.7 at% Au-WO3 nanofibers based sensor has higher sensing response toward MeSa, 1.1 at% Pt-WO3 nanofibers were found to be a more promising sensing material for MeSa detection because of higher selectivity over other VOCs and lower calculated LLOD ( ∼41 ppb).

Mechanically Enhanced Detoxification of Chemical Warfare Agent Simulants by a Two-Dimensional Piezoresponsive Metal-Organic Framework.

Chemical warfare agents (CWAs) refer to toxic chemical substances used in warfare. Recently, CWAs have been a critical threat for public safety due to their high toxicity. Metal-organic frameworks have exhibited great potential in protecting against CWAs due to their high crystallinity, stable structure, large specific surface area, high porosity, and adjustable structure. However, the metal clusters of most reported MOFs might be highly consumed when applied in CWA hydrolysis. Herein, we fabricated a two-dimensional piezoresponsive UiO-66-F4 and subjected it to CWA simulant dimethyl-4-nitrophenyl phosphate (DMNP) detoxification under sonic conditions. The results show that sonication can effectively enhance the removal performance under optimal conditions; the reaction rate constant k was upgraded 45% by sonication. Moreover, the first-principle calculation revealed that the band gap could be further widened with the application of mechanical stress, which was beneficial for the generation of 1O2, thus further upgrading the detoxification performance toward DMNP. This work demonstrated that mechanical vibration could be introduced to CWA protection, but promising applications are rarely reported.

In-situ adsorption and detoxification of chemical warfare agent simulants by biocompatible Zr-MOFs immobilized ionic liquids composites: Mechanisms, degradation pathways and DFT calculations

Detoxicating materials of chemical warfare agents (CWAs) and their simulants play a critical role in reducing pollution contamination and environmental renovation. In this work, we present a simple strategy to prepare a core–shell structure Fe3O4/UiO-66-NH2/ILs@mSiO2 using hydrogen bonding association and electrostatic forces. We performed disinfection studies on dimethyl 4-nitrophenyl phosphate (DMNP) and 2-chloroethyl ethyl sulfide (2-CEES). The synergistic effects of catalytic activations for CWAs, which reduce the electron transport distance and lower the reaction energy barrier, lead to an increase in hydrolysis and Fenton-like reactions efficiency. Eliminationing tests of DMNP and 2-CEES showed that the half-lives of the degradation reactions were 128.36 and 1.12 min, respectively, and the degradation efficiency did not decrease significantly after 4 cycles. This new type of structure could be magnetically separated within 60 s to facilitate material recovery and reuse. Moreover, the presence of a mesoporous silica shell made the catalyst particles to become biocompatible and environmentally friendly. The degradation pathways of the intermediates were revealed based on nuclear magnetic resonance spectroscopy (NMR), gaschromatography-mass spectrometry (GC–MS) and density functional theory (DFT) calculations. The effective combination of catalysts provided a facile strategy for developing multi-effect synergistic catalysts for the elimination of CWAs and other pollutants.

Thermodynamic Insights into Phosphonate Binding in Metal-Azolate Frameworks.

Organophosphorus chemicals, including chemical warfare agents (CWAs) and insecticides, are acutely toxic materials that warrant capture and degradation. Metal-organic frameworks (MOFs) have emerged as a class of tunable, porous, crystalline materials capable of hydrolytically cleaving, and thus detoxifying, several organophosphorus nerve agents and their simulants. One such MOF is M-MFU-4l (M = metal), a bioinspired azolate framework whose metal node is composed of a variety of divalent first-row transition metals. While Cu-MFU-4l and Zn-MFU-4l are shown to rapidly degrade CWA simulants, Ni-MFU-4l and Co-MFU-4l display drastically lower activities. The lack of reactivity was hypothesized to arise from the strong binding of the phosphate product to the node, which deactivates the catalyst by preventing turnover. No such study has provided detailed insight into this mechanism. Here, we leverage isothermal titration calorimetry (ITC) to monitor the binding of an organophosphorus compound with the M-MFU-4l series to construct a complete thermodynamic profile (Ka, ΔH, ΔS, ΔG) of this interaction. This study further establishes ITC as a viable technique to probe small differences in thermodynamics that result in stark differences in material properties, which may allow for better design of first-row transition metal MOF catalysts for organophosphorus hydrolysis.

Enhancing the degradation efficiency of dimethyl nitrophenyl Phosphate, a chemical warfare agent Simulant, through acid sites in bimetallic Metal-Organic framework Ti-MOF-808(Zr): Synergistic roles of Lewis and Brønsted acids

Nerve agents pose an immediate and severe threat to human health, emphasizing the critical need for catalysts that can rapidly and effectively degrade these agents. Herein, we synthesized Ti-MOF-808(Zr) materials with varying Ti/Zr molar ratio using microwave-assisted solvothermal method. Characterization techniques, including BET analysis, TEM, and TG-DTA, confirmed their outstanding properties, such as a high surface area (1756 m2/g), 100 nm particle size, cubic shape, and remarkable thermal stability exceeding 500 °C. The coexistence of Ti4+ and Zr4+ in the secondary building units or inorganic nodes significantly elevates the number of Lewis and Brønsted acid sites in the bimetallic Ti-MOF-808(Zr), as determined through the TPD-NH3 and FTIR-CD3CN methods. We harnessed the potential of MOF-808(Zr) and Ti-MOF-808(Zr) materials as catalysts for the swift degradation of dimethyl nitrophenyl phosphate (DMNP). Remarkably, 4 %Ti-MOF-808(Zr) could degrade DMNP with a half-life of 14.95 s, achieving a complete degradation time within 80 s. We conducted a comprehensive investigation into various factors affecting the DMNP degradation process, including the Ti/Zr molar ratio, catalyst mass, pH, and buffer solution concentration. Notably, our findings reveal that the efficiency of DMNP degradation is profoundly influenced by both the total number of Lewis acid sites and the average acid sites ratio.

Toward Remote Detection of Chemical Warfare Simulants Using a Miniature Potentiostat

A miniaturized electrochemical sensor was developed for the remote detection of chemical warfare agent (CWA) simulants. To facilitate drone-based remote sensing, this present study focuses on advancing the miniaturized and compact electrochemical sensor for monitoring two CWA simulants, diisopropyl fluorophosphate (DFP) and O,S-diethylmethylphosphonothioate (O,S-DEMPT). The differential pulse voltammetry (DPV) signal was processed, and the DPV signature features were extracted on the basis of the redox properties associated with the absence and the presence of DFP and O,S-DEMPT. Upon the addition of 0.10 equivalence of DFP or O,S-DEMPT, a shift in potential (E) of ~0.13 V was recorded. The limit of detection (LOD) was calculated to be 0.25 µM (0.046 ppm) and 0.10 µM (0.017 ppm) for DFP and O,S-DEMPT, respectively. These results were validated using a portable Palmsens Emstat HR potentiostat, which corroborated the results obtained using a lab benchtop potentiostat. Additionally, Boolean logic (“AND” operation) was implemented for future drone technology deployment. This advancement enables the fabrication of a networked device capable of autonomously executing tasks without constant oversight.

Decontamination coupled with dynamic adsorption of sulfur mustard (CEES) and nerve agent-sarin simulants (DMMP) on synthesized zeolite-alpha with its metal oxide composites

Chemical warfare agents (CWAs) are the most feared toxic chemicals intended to debilitate the general human population and regional civilians. Therefore, prompt and urgent decontamination is needed to protect millions of lives and the associated hazardous implications. In this present study, our main goal is to evaluate the performance of Zeolite-Alpha and its various metal oxide composites as novel adsorbents for the decontamination of CWA simulants, 2-chloroethyl ethyl sulfide (CEES), and dimethyl methyl phosphonate (DMMP). Synthesized Zeolite-Alpha and their composites were characterized by XRD, FTIR, SEM-EDS, and BET analysis techniques. The CWA simulants’ decontamination (adsorption and desorption) was monitored using GC-FID and GC-MS analysis techniques. A possible reaction mechanism toward the adsorption and destruction of CWA simulants, CEES, and DMMP was also proposed. Nanocrystalline Zeolite-Alpha and its metal oxide composites are powerful adsorbents, and they showed more significant decontamination potential toward the above CWA simulants. The Cr-O-Alpha and Ag-O-Alpha showed promising results (93–98% decontamination) among all other synthesized metal oxide composites.

Three-Dimensional Au Octahedral Nanoheptamers: Single-Particle and Bulk Near-Field Focusing for Surface-Enhanced Raman Scattering.

Herein, we present a synthetic approach to fabricate Au nanoheptamers composed of six individual Au nanospheres interconnected through thin metal bridges arranged in an octahedral configuration. The resulting structures envelop central Au nanospheres, producing Au nanosphere heptamers with an open architectural arrangement. Importantly, the initial Pt coating of the Au nanospheres is a crucial step for protecting the inner Au nanospheres during multiple reactions. As-synthesized Au nanoheptamers exhibit multiple hot spots formed by nanogaps between nanospheres, resulting in strong electromagnetic near-fields. Additionally, we conducted surface-enhanced Raman-scattering-based detection of a chemical warfare agent simulant in the gas phase and achieved a limit of detection of 100 ppb, which is 3 orders lower than that achieved using Au nanospheres and Au nanohexamers. This pseudocore-shell nanostructure represents a significant advancement in the realm of complex nanoparticle synthesis, moving the field one step closer to sophisticated nanoparticle engineering.

Halogen bonding BODIPY-appended pillar[5]arene for the optical sensing of dicarboxylates and a chemical warfare agent simulant.

A pillar[5]arene host, functionalised with halogen bonding (XB) recognition sites and BODIPY fluorophores, demonstrates strong binding and optical sensing of environmentally relevant dicarboxylates and a chemical warfare agent simulant, in organic and competitive aqueous-organic media - enabled by the unprecedented combination of fluorophore-conjugated XB interactions with the hydrophobic pillar[5]arene host cavity.

Green synthesis of MOF-based textile composites for the degradation of a chemical warfare agent simulant.

A green synthesis of UiO-66-NH2 embedded in chitosan and deposited on textiles has been investigated for the degradation of chemical warfare agents. This method requires no heating or use of toxic solvents. The composite synthesized presents an interesting efficiency in detoxifying common simulants of chemical warfare agents, such as DMNP. In parallel, resistance and permeability tests were also realized in order to confirm the suitability of the composites for further applications.

MOFabric: an effective and wearable protective garment towards CWA detoxification.

In current trends, an imminent development of self-detoxification filters is highly desirable against exposure to chemical warfare agents (CWAs). Exploiting protective materials that can be applicable in day-to-day life for instantaneous detoxification will be of immense importance. The available technologies in the current scenario are susceptible to secondary emission and pose a need for an alternate design strategy for effective degradation. In addition, the choice of active material and successful impregnation on a suitable substrate for developing potential barriers requires complex material design. In this context, the developed self-standing UiO-66 and UiO-66-NH2 functionalized fabrics (MOFabrics) present an expeditious detoxification performance against CWA simulant, methyl-paraoxon, with a maximum removal percent conversion of 88.9 and 90.68%. It shows a reduced half-life of approximately 10.16 and 11.23 min, in comparison to an unmodified/carboxymethylated fabric of 462 min.

Coordination-cage binding and catalysed hydrolysis of organophosphorus chemical warfare agent simulants.

The use of organophosphorus chemical warfare agents still remains an ongoing global threat. Here we investigate the binding of small-molecule organic guests including phosphate esters, sulfonate esters, carbonate esters and a sulfite ester - some of which act as simulants for organophosphorus chemical warfare agents - in the cavity of a water-soluble coordination cage. For several of these guest species, binding constants in the range 102 to 103 M-1 were determined in water/DMSO (98 : 2 v/v) solution, through a combination of fluorescence and 1H NMR spectroscopy, and subsequent fitting of titration data to a 1 : 1 binding isotherm model. For three cage/guest complexes crystallographic structure determinations were possible: in two cases (with guests phenyl methanesulfonate and phenyl propyl carbonate) the guest lies inside the cavity, forming a range of CH⋯O hydrogen-bonding interactions with the cage interior surface involving CH groups on the cationic cage surface that act as H-bond donors and O atoms on the guests that act as H-bond acceptors. In a third case, with the guest 4-nitrophenyl-methanesulfonate, the guest lies in the spaces outside a cage cavity between cages and forms weak CH⋯O interactions with the cage exterior surface: the cavity is occupied by a network of H-bonded water molecules, though this guest does show cavity binding in solution. For the isomeric guests 4-nitrophenyl-methanesulfonate and 4-nitrophenyl methyl sulfite, hydrolysis in water/DMSO (98 : 2 v/v) could be monitored colorimetrically via appearance of the 4-nitrophenolate anion; both showed accelerated hydrolysis rates in the presence of the host cage with second-order rate constants for the catalysed reactions in the range 10-3 to 10-2 M-1 s-1 at pH 9. The typical rate dependence on external pH and the increased reaction rates when chloride ions are present (which can bind inside the cavity and displace other cavity-bound guests) imply that the catalysed reaction actually occurs at the external surface of the cage rather than inside the cavity.

Self-driven microplasma decontaminates chemical warfare agent simulant in different gas environments

To develop and refine a self-driven plasma decontamination system, this study investigated the effect of different gas environments (air, Ar, Ar/O2, and Ar/O2/H2O) on the degradation efficiency of 2-chloroethyl ethyl sulfide (2-CEES). A dielectric-dielectric rotating triboelectric nanogenerator (dd-rTENG) was constructed to mechanically induce atmospheric plasma. The dominant active species of different plasmas were identified through spectroscopic and chemical probe diagnostic methods. The results revealed that Ar/O2 and Ar/O2/H2O plasmas generated higher levels of reactive Ox species (O3, O2-, and 1O2) and OH radicals, respectively. Notably, the Ar/O2 and Ar/O2/H2O plasmas exhibited significantly higher decontamination efficiencies than the other plasmas. Moreover, the Ar/O2/H2O plasma featured an energy utilization efficiency of 0.962 μg/J, which is nearly twice that of the previously reported study. However, the Ar plasma exhibited minimal decontamination effect owing to its low electron energy and absence of active species. Further studies have indicated the vital role of reactive oxygen species in the 2-CEES decontamination process. Active Ox can promote the oxidation of 2-CEES, while OH can effectively mitigate the peroxidation process. Furthermore, the system exhibited low electron energy, which might play small role for 2-CEES decontamination. This study is vital for developing self-driven plasma decontamination devices and provides significant clues for understanding the 2-CEES decontamination mechanism.

Rapid Oxidative Detoxification of Mustard Simulant by the Multisite Synergistic Catalytic Action of {PMoVI11MoVO40CuI8} Units.

Under hydrothermal and solvent-thermal conditions, we synthesized two novel polyoxometalate (POM)-based hybrids: [CuI4(Pz)2(H2O)8(PMoVI11MoVO40)]·3.5H2O (1, Pz = pyrazine) and [(C2H8N)5(HPMoVI9MoV3O40)]·DMF·4H2O (2). Single-crystal X-ray diffraction indicates that compound 1 is a three-dimensional structure consisting of Cu (I), {PMo12} anions, Pz, and water, where Cu (I) can be considered as Lewis acid sites. Furthermore, both compounds 1 and 2 possess favorable catalysis activity in catalyzing the conversion of chemical warfare agent simulant 2-chloroethylethyl sulfide (CEES) to nontoxic production of 2-chloroethylethyl sulfoxide (CEESO) under ambient temperature. Significantly, 1 could realize 98% conversion and 100% selectivity of CEES owing to the multisite synergy in the {PMoVI11MoVO40CuI8} units in which the tricoordinated Cu (I) could interact with S and O atoms from CEES and H2O2, respectively. This interaction not only decreases the distance of CEES from peroxomolybdenum species formed by H2O2 but also activates CEES.