Simulant Dimethyl Methylphosphonate Research Articles

Two-dimensional photonic crystal sensor enabled by hydrophobic hydrogen-bonded organic Frameworks@Metal-Organic frameworks for trace nerve agents detection

The development of fast and accurate sensors for nerve agents holds immense significance for homeland security and public health. However, the humidity interference from ambient environments and poor sensitivity for trace nerve agents are largely unsolved problems. To overcome the problems, a humidity-independent two-dimensional photonic crystal (2-D PC) sensor is developed by exploiting UiO-66-NH2 2-D PC with excellent sensitivity coupled to a hydrophobic hydrogen-bonded organic framework (HOFs) for detection sarin simulant dimethyl methyl phosphonate (DMMP). Selective sensing results show that the HOFs@UiO-66-NH2 2-D PC sensor presents the outstanding DMMP specificity, and the limit of detection (LOD) for DMMP response of the sensor can reach 508 ± 68 ppb at room temperature. Water-resistant experiments demonstrate that the HOFs@UiO-66-NH2 2-D PC sensor shows excellent stability even under 80% relative humidity (RH). Moreover, the sensor also exhibits a rapid response/recovery time of 1 s/3 s and can maintain excellent sensing performance under heat-treatment of 200 °C and in the long-term storage (30 days). The adsorption kinetics and the hydrogen bond interaction are conducted to elucidate the mechanism of enhanced sensing DMMP properties. These results indicate the potential application of the sensor in the trace nerve agent's detection, especially in humidity environment.

The Application of Microfibrous Entrapped Activated Carbon Composite Material for the Sarin Simulant Dimethyl Methylphosphonate Adsorption.

Granular activated carbon (GAC) has proven to be an effective adsorbent for removing the chemical warfare agent sarin (GB) and simulants like Dimethyl methylphosphonate (DMMP). However, it comes with certain limitations, including inadequate contact efficiency, notable mass transfer resistance, and lower bed utilization efficiency. This study synthesized steel fiber-entrapped activated carbon composites (SFEACs), which exhibited a maximum adsorption capacity of 285.3 mg/g at 303 K. Compared with the packed bed (PB) filled with GAC, while the adsorption capacity of SFEACS decreased, there was a substantial increase in the adsorption mass transfer rate. These SFEACs were combined with GAC to create a structural fixed bed (SFB), which demonstrated excellent performance in DMMP removal. Under identical experimental conditions, the DMMP breakthrough curve of SFB exhibited a steeper profile compared to the packed bed (PB) filled with GAC at the same bed height, and the breakthrough time against DMMP vapor could be extended by 13.8%. Furthermore, the adsorption rate constant of the Yoon-Nelson model increased by more than 17.6%, and the unused bed length, according to the Wheeler-Jonas model, decreased by more than 14%.

Hydrogen-bond acidic organic compound-sensitized ionic gel for dimethyl methylphosphonate detection

Due to the threat of chemical warfare agents (CWAs), there is a pressing need to develop miniaturized gas sensors with fast response, high sensitivity and good stability. Herein, hexafluoroisopropanol aniline (HFIPA), a hydrogen-bond acidic organic compound, is embedded into a cross-linked poly(ethylene glycol) diacrylate/ionic liquid (PEGDA/IL) matrix as a sensitive film for detecting sarin simulant dimethyl methylphosphonate (DMMP). We find that the IL in the film constructs efficient gas transport channels, improving the absorption-desorption kinetics of DMMP molecules. The introduction of HFIPA enhances selectivity and sensitivity to DMMP through hydrogen bonding interaction. As a result, the SAW gas sensor based on PEGDA/IL-HFIPA ionic gel exhibits a fast response/recovery time of 28/53 s to 20 ppm DMMP and a low detection limit of 0.2 ppm at room temperature. By comparing with PEGDA-HFIPA, PEGDA/IL-HFIPA shows excellent anti-humidity interference ability, which is also attributed to the stable gas transport channels constructed by IL. Overall, this work develops a novel strategy to improve the gas-sensing properties of organic polymer materials.

Chitosan-Based Molecularly Imprinted Polymers for Effective Trapping of the Nerve Agent Simulant Dimethyl Methylphosphonate

A molecular imprinted polymer (MIP) fabricated from a biomaterial (chitosan) was successfully created for the selective trapping of dimethyl methylphosphonate (DMMP) in the thousands of parts per million. DMMP is an organophosphorus compound that can be used in the production of chemical weapons and is the accepted surrogate to test filters and protective clothing designed to trap organophosphorus compounds. Computational calculations (density functional theory: B3LYP/6-31G) were used to calculate the optimum ratio of chitosan to DMMP that would produce the most energetically stable template–monomer complex. Gas chromatography mass spectrometry was used to model the DMMP concentration in the gas phase and to determine the DMMP trapped by the MIP, non-imprinted polymer (NIP), and activated charcoal. The MIP trapped 4554 (±227) ppm (4.55 mg/g) DMMP and outperformed both the NIP (156 (±20) ppm (0.16 mg/g)) and activated charcoal (82 (±17) ppm (0.08 mg/g)). Acetic acid, ammonium hydroxide, acetone, ethanol, and 2-propanol were introduced into the system as interferents and did not significantly affect the amount of DMMP trapped by the MIP: 4286 (±74) ppm (4.29 mg/g). Reusability of the MIP is affected by the extraction process but does not significantly affect the intended use as a filter for hazardous materials. Scanning electron microscopy was used to study the surface morphology of the MIP, and after MeOH extraction, the surface of the MIP became coarser, illustrating the alteration of the material. Overall, the trapping capabilities of the MIP are far superior to activated charcoal 50-fold and can be used as a filling agent in gas masks or gas filters.

Insights and Heuristics for Predicting Diffusion Rates of Chemical Warfare Agents in Zirconium Metal-Organic Frameworks.

Designing nanoporous catalysts to destroy chemical warfare agents (CWAs) and environmental contaminants requires consideration of both intrinsic catalytic activity and the mass transfer of molecules in and out of the pores. Polar adsorbates such as CWAs experience a heterogeneous environment in many metal-organic frameworks (MOFs) due to the arrangement of the metal nodes and organic linkers of the MOF. However, quantitative relationships between the pore architecture and the resulting diffusion properties of polar molecules have not been established. We used molecular dynamics simulations to calculate the diffusion coefficients of the CWA simulant dimethyl methyl phosphonate (DMMP) in a diverse set of 776 MOFs with Zr6 nodes. We developed a 4-parameter machine learning model to predict DMMP diffusivities in Zr6 MOFs and found the model to be transferable to the CWA sarin. We then developed a simplified heuristic based on the machine learning model that the node-node distance and accessible surface area should be maximized to find MOFs with rapid CWA diffusion.

Rational Design of a Zr-MOF@Curli-Polyelectrolyte Hybrid Membrane toward Efficient Chemical Protection, Moisture Permeation, and Catalytic Detoxification.

Developing high-performance protective materials is important for soldiers and civilians who are exposed to the atmosphere of highly toxic chemical warfare agents (CWAs). Polyelectrolyte membranes are promising candidates with excellent chemical resistance and moisture permeability, but they cannot efficiently degrade CWAs. Here, we design and prepare a hybrid membrane through in situ growth of catalytically active zirconium-based metal-organic frameworks (Zr-MOFs) on a polyelectrolyte membrane mediated by biofilm-inspired curli nanofibers (CNFs). Superior to the bare polyelectrolyte membrane, the prepared MOF-808@CNF-PQ hybrid membrane exhibits improved rejection of the nerve agent simulant dimethyl methyl phosphonate (DMMP) vapor and permeation of the water vapor by 113 and 45%, respectively. The water/DMMP selectivity of the hybrid membrane reaches 498.6, approximately 13 times that of the commercial polyelectrolyte membrane Nafion 117. In addition, the hybrid membrane possesses appreciable catalytic activity for the hydrolysis of the nerve agent simulant dimethyl 4-nitrophenyl phosphate (DMNP) with a half-life of ∼38 min. Nanomechanical characterization results based on atomic force microscopy (AFM) techniques demonstrate the critical role of CNFs in mediating Zr-MOF nucleation and the dominant effect of electrostatic interactions on self-assembly of CNFs on polyelectrolyte base. It is also confirmed that the Zr-MOF toppings serve as the key components in physically adsorbing and chemically degrading the DMNP molecules through multiple strong intermolecular interactions. Our work offers a rational strategy to develop advanced membranes toward efficient chemical protection, moisture permeation, and catalytic detoxification against CWAs.

Catalytic Oxidative Decomposition of Dimethyl Methyl Phosphonate over CuO/CeO2 Catalysts Prepared Using a Secondary Alkaline Hydrothermal Method

Bimetallic synergism plays an important role in lattice-doped catalysts. Therefore, lattice-doped bimetallic CuO/CeO2 catalysts were prepared by secondary alkaline hydrothermal reaction. During this process, the CeO2 nanomaterials were partially dissolved and recrystallized; thus, Cu ions were doped into the CeO2 lattice. The physical and chemical properties of CeO2, CuO/CeO2, and CuO were investigated. H2 temperature-programmed reduction characterization showed that the oxidation activity of CuO/CeO2 was significantly improved. X-ray photoelectron spectroscopy results showed that electron transfer occurred between Ce and Cu in the CuO/CeO2 catalyst. Additionally, Raman characterization confirmed the strong interaction between Cu and Ce. After CuO was loaded, the thermal catalytic decomposition performance of the catalyst was significantly improved with respect to the sarin simulant dimethyl methyl phosphonate (DMMP); with an increase in the Cu/Ce ratio, the performance first strengthened and then weakened. Additionally, the reaction tail gas and catalyst surface products were analyzed using mass spectrometry and ion chromatography, and the changes in the surface products during the thermal catalytic decomposition of DMMP were characterized at different temperatures using in situ diffuse reflectance infrared Fourier transform spectroscopy. Finally, the catalytic reaction pathways of DMMP on CeO2, CuO/CeO2, and CuO were inferred. The study results not only demonstrate an effective catalyst for the removal of nerve agent but also a feasible preparation method for lattice-doped bimetallic catalysts in the field of environmental protection.

Thermal Catalytic Decomposition of Dimethyl Methyl Phosphonate Using CuO-CeO2/γ-Al2O3

Chemical warfare agents (CWAs) are highly toxic and fast-acting and are easy to cause large-scale poisoning to humans and livestock after being released. The activated carbon used for CWAs adsorption has disadvantages of limited adsorption capacity, easy aging and deactivation. Metal oxides have environmental stability, and they are characterized by long lasting and broad spectrum when used for thermal catalytic decomposition. Therefore, in this study, the supported copper–cerium catalyst CuO-CeO2/γ-Al2O3 was prepared using an equal volume impregnation method. The thermal catalytic decomposition performance was studied using sarin CWAs simulant dimethyl methyl phosphonate (DMMP) as the target compound. The results show that the CuO-CeO2/γ-Al2O3 catalyst with a CeO2 loading of 5% exhibited better thermal catalytic decomposition performance of DMMP. The catalyst provided protection against DMMP for 237 min at 350 °C; CuO was highly dispersed on CuO-5% CeO2/γ-Al2O3, and there was a strong interaction between Cu and Ce on CuO-5% CeO2/γ-Al2O3, which promoted the generation of surface-adsorbed oxygen, leading to a better thermal catalytic decomposition performance of DMMP. This study is expected to provide a reference for the study of catalysts for the thermal catalytic decomposition of CWAs.

In situ encapsulation of ZrQ in UiO‐66 (Zr‐BDC) for pore size control to enhance detection of a nerve agent simulant dimethyl methyl phosphonate

Chemical warfare agents are toxic chemicals that require rapid, easy‐to‐use, sensitive, and selective sensors to countermeasure. Simulants, such as dimethyl methyl phosphonate (DMMP), are used to test the effectiveness of sensors toward nerve agents. Metal organic frameworks (MOFs) offer large surface area and selective accessibility to active sites making them appealing for chemical sensing applications. In this work, we propose a fast, facile, direct synthesis method for manufacturing fluorescent MOFs with high sensitivity and selectivity. Zr‐BDC is synthesized with 1, 4‐benzenedicarboxylic acid (BDC) as an organic ligand and zirconium (Zr) metal. Fluorescent materials are then encapsulated in a novel and rapid in situ approach with strong solvents. X‐ray diffraction, UV–visible spectroscopy, Fourier‐transform infrared spectroscopy, and Raman spectroscopy are used to verify the successful formation of fluorescent MOFs. Compared to other methods, the gel synthesis method helps to control crystal growth leading to higher BET surface areas of ~1150 m2 g−1 for Zr‐BDC and 850 m2 g−1 for ZrQ@Zr‐BDC. Titration experiments show the sensitivity of the material to DMMP down to 8.3 nM with a highly linear response. Enhanced fluorescence and occupation of mesopores by ZrQ enable lower limit of detection than those of comparable works in literature. The encapsulation mechanism also prevents substantial defects that would otherwise lead to water adsorption.

Study on the formulations for Topical Skin Protectant against Liquid-Phase Chemical Warfare Agents

Chemical warfare agents(CWA) such as nerve agents and vesicating agents show lethality by skin contamination. Skin protection, therefore, is one of the top priorities to deal with the growing threat from CWA. In an attempt to develop the most effective topical skin protectant(TSP), candidate substances including PFPE(perfluorinated polyether), PTFE(polytetrafluoroethylene), glycerin, and polysaccharides were evaluated in forms of various formulations against nerve agent simulant DMMP(dimethylmethyl phosphonate) penetration. The protective efficacy of the formulation against DMMP penetration was estimated as the onset time of color change of the KM9 chemical agent detection paper. Based on this study, it was found that several PFPE- and glycerin-based formulations exhibit remarkably superior efficacy as a protective cream. This protective cream is expected to be used as TSP for military application after further research.

Insects as Chemical Sensors: Detection of Chemical Warfare Agent Simulants and Hydrolysis Products in the Blow Fly Using LC-MS/MS.

In this work, blow flies were investigated as environmental chemical sample collectors following a chemical warfare attack (CWA). Blow flies sample the environment as they search for water and food sources and can be trapped from kilometers away using baited traps. Three species of blow flies were exposed to CWA simulants to determine the persistence and detectability of these compounds under varying environmental conditions. A liquid chromatography mass spectrometry (LC-MS/MS) method was developed to detect CWA simulants and hydrolysis products from fly guts. Flies were exposed to the CWA simulants dimethyl methylphosphonate and diethyl phosphoramidate as well as the pesticide dichlorvos, followed by treatment-dependent temperature and humidity conditions. Flies were sacrificed at intervals within a 14 day postexposure period. Fly guts were extracted and analyzed with the LC-MS/MS method. The amount of CWA simulant in fly guts decreased with time following exposure but were detectable 14 days following exposure, giving a long window of detectability. In addition to the analysis of CWA simulants, isopropyl methylphosphonic acid, the hydrolysis product of sarin, was also detected in blow flies 14 days post exposure. This work demonstrates the potential to obtain valuable samples from remote or access-restricted areas without risking lives.

Synthesis of Novel CuO/ZnFe2O4/NaA Zeolite Nanocomposite Adsorbent for the Decontamination of Nerve Agent Sarin Simulant

The aim of present research is to evaluate the decontamination of nerve agent sarin simulant dimethyl methyl phosphonate (DMMP) in water media using the CuO/ZnFe2 O4 /NaA zeolite as a novel ternary nanocomposite adsorbent. In this regard, the CuO and ZnFe2 O4 nanoparticles were successfully synthesized within the NaA zeolite applying the ultrasound-assisted hydrothermal route and characterized via XRD, FESEM, FTIR, EDAX, VSM and BET analyses. Then, the CuO/ZnFe2 O4 /NaA nanocomposite activity was investigated for the decontamination of DMMP molecule and monitored by a GC-FID and GC-MS analyses. Plus, the impacts of several parameters, including contact time, adsorbent dose and adsorbent type on the decontamination of DMMP were studied. The gained data from GC-FID analysis confirmed the maximum decontamination more than 98.4% for DMMP. The parameters including: adsorbent amount of 50 mg and contact time of 40 min were achieved as the optimized values for the decontamination reaction. In addition, the non-toxic methyl phosphoric acid (MPA) as the DMMP degradation product in the presence of CuO/ZnFe2 O4 /NaA adsorbent was characterized.

Two high-nuclearity isopolyoxoniobates containing {Nb54 O151}-based helical nanotubes for the decomposition of chemical warfare agent simulants.

Two inorganic-organic hybrid isopolyoxoniobates (1 and 2) based on new high-nuclearity {Nb54O151} clusters have been synthesized under hydrothermal conditions. In particular, the combination of the unique {Nb54O151} clusters with copper-amine complexes has led to rare helical nanotubes, which are further linked by alkali metal cations or copper-amine complexes into two 2D similar bamboo-raft-like layered networks (1 and 2), respectively. Compound 1 exhibits effective base-catalytic decomposition of chemical warfare agent simulants dimethyl methylphosphonate (DMMP) and diethyl cyanophosphonate (DECP).

Force Fields for Molecular Modeling of Sarin and its Simulants: DMMP and DIMP.

Even three decades after signing the Chemical Weapons Convention, organophosphorus chemical warfare agents (CWAs), such as sarin, remain a threat. The development of novel methods for the detection of CWAs, protection from CWAs, and CWA decontamination motivates research on their physicochemical properties. Due to the extreme toxicity of sarin, most of the experimental studies are carried out using less toxic simulant compounds. In addition to experimental studies of sarin simulants, both sarin and simulants can be studied using in silico experiments-molecular simulations. The results of classical molecular modeling of the compounds and their agreement with experimental data rely on the force field used to describe the system. In recent years, there have been several force fields proposed for sarin and its most common simulant dimethyl methylphosphonate (DMMP). However, other simulants frequently used in experiments received less attention from the molecular simulation perspective, for example, to date, there is no force field and no simulation data for diisopropyl methylphosphonate (DIMP). Here, we compare the literature force fields for sarin and DMMP, focusing specifically on the vapor-liquid equilibrium for the pure species. We carried out Monte Carlo and molecular dynamics simulations using the existing literature force fields from which we predicted the liquid densities and vapor pressures developing the entire binodal curves. We compared the predictions to the experimental data and showed that the TraPPE-UA force field outperformed the other force fields. Thus, we extended TraPPE-UA for DIMP, utilized this force field in molecular simulations, and predicted the liquid densities and vapor pressures for a range of temperatures (binodal curve), which agreed well with the published experimental data. From the binodal, we calculated the critical properties of DIMP and demonstrated that these parameters can be used in the Peng-Robinson equation of state for this compound.

Graphene Oxide-Based Membrane as a Protective Barrier against Toxic Vapors and Gases.

Traditional protective garments loaded with activated carbons to remove toxic gases are very bulky. Novel graphene oxide (GO) flake-based composite lamellar membrane structure is being developed as a potential component of a garment for protection against chemical warfare agents (CWAs) represented here by simulants, dimethyl methyl phosphonate (DMMP) (a sarin-simulant), and 2-chloroethyl ethyl sulfide (CEES) (a simulant for sulfur mustard), yet allowing a high-moisture transmission rate. GO flakes of dimensions 300-800 nm, 0.7-1.2 nm thickness and dispersed in an aqueous suspension were formed into a membrane by vacuum filtration on a porous poly(ether sulfone) (PES) or poly(ether ether ketone) (PEEK) support membrane for noncovalent π-π interactions with GO flakes. After physical compression of such a membrane, upright cup tests indicated that it can block toluene for 3-4 days and DMMP for 5 days while exhibiting excellent water vapor permeation. Further, they display very low permeances for small-molecule gases/vapors. The GO flakes underwent cross-linking later with ethylenediamine (EDA) introduced during the vacuum filtration followed by physical compression and heating. With a further spray coating of polyurethane (PU), these membranes could be bent without losing barrier properties vis-à-vis the CWA simulant DMMP for 5 days; a membrane not subjected to bending blocked DMMP for 15 days. For the PEEK-EDA-GO-PU-compressed membranes after bending, the separation factors of H2O over other species for low gas flow rates in the dynamic moisture permeation cell (DMPC) are: αH2O-He is 42.3; αH2O-N2 is 110; and αH2O-ethane is 1800. At higher gas flow rates in the DMPC, the moisture transmission rate goes up considerably due to reduced boundary layer resistances and exceeds the threshold water vapor flux of 2000 g/(m2·day) that defines a breathable fabric. This membrane displayed considerable resistance to permeation by CEES as well. The PES-EDA-GO-PU-compressed membrane shows good mechanical property under tensile strength tests.

Study of Light-Activated Regioregular Poly(3-Hexyltiophene) Photoconductive Polymer Sensing Properties in Nerve Agent Simulant (DMMP) Detection†.

In the present work, we report the use of regioregular poly(3-hexyltiophene) polymer (RR-P3HT) as a potential light-activated material for sensing the chemical nerve agent simulant dimethyl methylphosphonate (DMMP). The electrical response of thick films of RR-P3HT, deposited by spray-coating method onto a porous laminate substrate at room temperature, to DMMP vapours was investigated. The studied material was activated by light-emitting diodes that emitted light of different wavelengths. The sensing properties of RR-P3HT are considerably enhanced upon exposure to blue and yellow light. However, excitation by the low wavelength light (blue) caused degeneration of the material, resulting in lowered stability. In the case of the yellow light, degeneration was much slower and the limit of detection was 0.4 ppm. The studied material exhibited high selectivity, as it did not respond to 6 ppm of acetone and methanol vapours.

Chitosan-Derived Porous Activated Carbon for the Removal of the Chemical Warfare Agent Simulant Dimethyl Methylphosphonate.

Methods for the rapid removal of chemical warfare agents are of critical importance. In this work, a porous activated carbon material (C-PAC) was prepared from chitosan flakes via single-step potassium carbonate (K2CO3) activation for the prompt adsorption of dimethyl methylphosphonate (DMMP). C-PAC samples were prepared using different carbonization temperatures (350, 550, and 750 °C) at a constant K2CO3/chitosan ratio (1:2) and using different activator ratios (K2CO3/chitosan ratios of 1:0.5, 1:1, 1:2, and 1:3) at 750 °C. Furthermore, we evaluated the effect of preparation conditions on the adsorption capacities of the various C-PAC materials for DMMP under ambient conditions (25 °C). Notably, for the C-PAC material prepared at 750 °C using a K2CO3/chitosan ratio of 1:2, the DMMP adsorption was saturated at approximately 412 mg·g−1 carbon after 48 h. The good performance of this material makes it a potential candidate for use in remedial applications or protective gear.

Hydrogen-bonding interactions in crown-(thio)urea complexes with anions, chemical warfare agents and simulants

ABSTRACTBenzocrown ethers incorporating phenyl and nitrophenyl urea and thiourea moieties were synthesised. Both the nitrophenyl urea and thiourea derivative gave a fluoride-specific colorimetric response but only the urea derivative bound the organophosphonate nerve agent simulants dimethyl methylphosphonate (DMMP) and diisopropyl methylphosphonate (DIMP). This suggested an application as sensors for the nerve agents sarin, soman and cyclosarin which release fluoride upon hydrolysis. Although no fluoride-induced response was observed in the UV-visible spectrum, binding to soman was determined by 1H NMR. DFT computational simulations suggested that the two crowns adopt different conformations in which both can bind fluoride but only the urea derivative can bind DMMP, DIMP and soman. The results show that, for this system, simulant- and soman-binding behaviours are in good agreement.

Computational Exploration of the Catalytic Degradation of Sarin and Its Simulants by a Titanium Metal–Organic Framework

The catalytic degradation of chemical warfare agents (CWAs) into nontoxic products by metal organic frameworks (MOFs) has been exclusively focused on Zr-based materials so far, although Ti-MOFs might be also of interest owing to the well-known capacity of Ti compounds to efficiently hydrolyze CWAs. Here, we report for the first time a computational exploration of several possible hydrolysis mechanisms on the activated Ti site of a recently discovered highly stable Ti-MOF, MIP-177(Ti), in the presence/absence of water, considering sarin and its simulants dimethyl methylphosphonate and diisopropyl phosphorofluoridate. Density functional theory calculations were performed at the periodic level to accurately assess the main states of the degradation reaction (reactants, transition states, and products) and the associated activation energy barriers for each degradation reaction that are further compared to the corresponding data previously reported for Zr-MOFs. MIP-177(Ti) was demonstrated to be a promising candidate for an efficient degradation of sarin and retention of the resulting products with a level of performance as attractive as that of the best Zr-MOFs reported so far. Furthermore, the simulations performed on the two simulants emphasized that diisopropyl phosphorofluoridate better mimics sarin in terms of the transition states and products obtained during the reaction as well as of the activation energy required to achieve their degradation.

Gas sensing with hexafluoroisopropanol substituted phthalocyanines andvic-dioximes: a comparative study

Phthalocyanines (Pcs) are established sensitive materials for chemical gas sensors due to their superb sensing characteristics and the achievable manifold in their analyte interaction properties. Their sorption properties are determined by the metal ion center and substituents attached to the periphery of the ring system. Similarly, vic-dioximes can be modified in their sorption properties and employed as sensitive materials. In this work, a nickel Pc and various vic-dioximes functionalized with the same hexafluoroisopropanol moiety are assessed and compared in their gas-sensing properties using the quartz crystal microbalance for the first time. This specific substituent is selected for its hydrogen bond acidity for strong interactions with analytes having corresponding sites. The synthesis and characterization of the new compounds are described. Sensor results are presented for ten selected organic compounds and the chemical warfare agent simulant dimethyl methylphosphonate (DMMP). Both compound classes exhibit good sensing performance but were found to exhibit very diverging analyte preferences, as preferential sorption of either amines or polar compounds was observed depending on the molecule type. Thus, by applying the same substituent to different base molecules, sensitive compounds with very distinct sensing properties can be realized.