One novel calix[4]arene based QCM sensor for sensitive, selective and high performance-sensing of formaldehyde at room temperature
Graphical abstract
Introduction
One of the volatile organic compounds (VOCs), formaldehyde (HCHO), is a toxic gas which can cause a serious problem such as cancer or other allergens for our life at even low concentration after long term exposure [1,2]. HCHO has been widely employed in various manufacturing processes such as in the production of industrial chemicals and adhesives, textile industry [3]. For this reason, both common usage of HCHO and it's being a volatile compound cause to release of it extremely to the environment. Thus, high sensitively and rapidly detection of HCHO is crucial to eliminate the adverse effects of it on both human and environmental health. For the detection of HCHO, lots of analytical detection methods such as gas chromatography [4,5], spectrometry [6,7], fluorimetry [8] and chemical gas sensors [[9], [10], [11]] have been employed. However, some of these methods have disadvantage such as requirements of HCHO samples collection and test in the laboratory. Among the above HCHO detection methods, QCM has received increasing attention because of high sensitivity, fast response, simplicity, low experimental cost, detectible mass changes at ng level and has been confirmed to be the most attractive and widespread technique for measuring HCHO at even low concentration [12]. QCM compose of a piezoelectric quartz crystal which can be modified and deposited by sensitive and selective materials as an adsorptive surface [13]. A number of QCM applications regarding VOCs were reported in the literature [[14], [15], [16], [17], [18]]. Till now, many sensitive materials such as metal complex [19], mesoporous [20], nanoparticles [21], polymers [22], hydrogels [23], and macromolecules [24] have been reported for gas emissions. Among organic macromolecules, calixarenes are known as one of the exciting classes due to being commonly used as an ideal molecular platform in many application such as sensing [25], adsorption [26], etc. Recently, we have focused on that calix[4]arene derivatives as sensing materials in QCM sensors such as biological applications as well as VOCs [13,[27], [28], [29], [30]].
In this work, my objective is primarily that the preparation of the new amino morpholine schiff base functionalized calix[4]arene cage (SCC) (Fig. 1A). Subsequently, it was coated onto the QCM sensor as the sensing material to get SCC modified QCM sensor (Fig. 1B). The sensing responses to HCHO were investigated at a range of concentrations. Initial experiments clearly demonstrated that this sensor exhibited high frequency responses towards HCHO. Furthermore, the analytical performance of this sensor was evaluated in terms of the limit of detection (LOD) and sensor sensitivity (S). Also, the adsorption models such as Langmuir, Freundlich, and Langmuir-Freundlich, and Scatchard were also applied to specify the adsorption behavior of HCHO. The selectivity of this sensor towards HCHO was compared to %97 RH and a number of interfering VOCs such as chloroform, dichloromethane, acetone, n-hexane, methanol, xylene, and ammonia. Consequently, the real-time and selective detection of HCHO was performed by SCC modified QCM sensor.
Section snippets
Chemicals
Sodium hydroxide (NaOH, >97.0% purity), formaldehyde (HCHO, 37.0% w/w), p-ter-butlyphenol (>98.0%), diphenylether (>98.0%), ethyl acetate (>99.8%), acetonitrile (CH3CN, >99.9%), iodomethane (CH3I, >99.0%), potassium carbonate (K2CO3, >99.0%), hexamethylenetetramine (HMTA, >99.0%), trifluoroaceticacid (TFA, 24.5–25.5%), chloroform (CHCl3, >99.0%), and 4-aminomorpholine (>97%) were purchased from Merck and Sigma-Aldrich company to synthesize p-tert-butylcalix [4]arene and its derivatives. All
Synthesis and characterization of calix[4]arene derivatives
In this work, schiff base functionalized calix[4]arene cage (SCC) having amino morpholine was synthesized in order to investigate its sensing ability towards HCHO through the QCM method. The synthesis of compound 1–3 was carried out according to previous literature methods [[31], [32], [33]]. All synthesized compounds were characterized by a variety of spectroscopic techniques such as FT-IR and 1H NMR. First of all, p-tert-butylcalix[4]arene (1) was reacted with iodomethane in acetonitrile to
Conclusions
In conclusion, the amino morpholine schiff base functionalized calix[4]arene cage (SCC) has been synthesized as the novel, characterized by FTIR, 1H NMR and other methods above mentioned, and deposited onto the QCM sensor. The sensor surface and morphology were characterized by using contact angle and microscopic images. After that, the proposed sensor was used for the sensing or detection of HCHO at ppm-level. The frequency response values were recorded towards HCHO in different
Acknowledgments
The author would like to thank Prof. Mustafa TABAKCI for providing laboratory facilities. I am grateful for the financial support from the Research Foundation of Konya Technical University.
References (47)
- et al.
One novel humidity-resistance formaldehyde molecular probe based hydrophobic diphenyl sulfone urea dry-gel: synthesis, sensing performance and mechanism
Sens. Actuators B Chem.
(2017) - et al.
Highly sensitive gaseous formaldehyde sensor with CdTe quantum dots multilayer films
Biosens. Bioelectron.
(2009) - et al.
Microbottle resonator for formaldehyde liquid sensing
Optik
(2018) - et al.
Detection and analysis of formaldehyde and unburned methanol emissions from a direct-injection spark-ignition methanol engine
Fuel
(2018) - et al.
A rapid, simple method for determining formaldehyde in drinking water using colorimetric-solid phase extraction
Talanta
(2009) - et al.
A simple spot test quantification method to determine formaldehyde in aqueous samples
J. Saudi Chem. Soc.
(2016) - et al.
A sensitive flow analysis system for the fluorimetric determination of low levels of formaldehyde in alcoholic beverages
Talanta
(2007) - et al.
Controlled synthesis of porous Ni-doped SnO2 microstructures and their enhanced gas sensing properties
J. Alloy. Comp.
(2017) - et al.
Perovskite-type ZnSn(OH)6 hollow cubes with controllable shells for enhanced formaldehyde sensing performance at low temperature
Sens. Actuators B Chem.
(2019) - et al.
High-performance formaldehyde adsorption on CuO/ZnO composite nanofiber coated QCM sensors
J. Alloy. Comp.
(2019)
QCM formaldehyde sensing materials: design and sensing mechanism
Sens. Actuators B Chem.
Sensing abilities of functionalized calix[4]arene coated QCM sensors towards volatile organic compounds in aqueous media
Appl. Surf. Sci.
Calix[4]arene coated QCM sensors for detection of VOC emissions: methylene chloride sensing studies
Talanta
PODS-covered PDA film based formaldehyde sensor for avoiding humidity false response
Sens. Actuators B Chem.
High performance formaldehyde detection based on a novel copper (II) complex functionalized QCM gas sensor
Sens. Actuators B Chem.
Synthesis of mesoporous SnO2–SiO2 composites and their application as quartz crystal microbalance humidity sensor
Sens. Actuators B Chem.
Recent progress in metal-organic frameworks-based hydrogels and aerogels and their applications
Coord. Chem. Rev.
A novel triazine‒bearing calix[4]arene: design, synthesis and gas sensing affinity for volatile organic compounds
Tetrahedron
Adsorption of phenolic compounds onto calix[4]arene-bonded silica gels from aqueous solutions
React. Funct. Polym.
A phenyl glycinol appended calix[4]arene film for chiral detection of ascorbic acid on gold surface
Anal. Biochem.
Rapid and real-time detection of arginine enantiomers by QCM sensor having a Calix[4]arene receptor bearing asymmetric centers
Talanta
Synthesis and application of an efficient calix[4]arene-based anion receptor bearing imidazole groups for Cr(VI) anionic species
Tetrahedron
Calix[4]arene-based Mannich and Schiff bases as versatile receptors for dichromate anion extraction: synthesis and comparative studies
Tetrahedron
Cited by (26)
Unleashing the potential of QCM: A comprehensive review of aptamer-based QCM sensing analysis
2024, Microchemical JournalLa-Ce-MOF nanocomposite coated quartz crystal microbalance gas sensor for the detection of amine gases and formaldehyde
2024, Journal of Hazardous MaterialsHydrogen adsorption and sensing properties of p-tert-butylcalix[4]arene and its transition metal complexes: A DFT study
2023, International Journal of Hydrogen EnergyDesign of long-term stable formaldehyde sensor and its humidity enhanced sensing effect
2023, Sensors and Actuators A: PhysicalCitation Excerpt :After the sensitive material is coated on the QCM chip and adsorbs the target gases, its mass change can be sensitively recorded [8,9]. Now the sensitizing materials for HCHO detection are mainly organic polymers, such as diphenyl sulfone urea dry-gel, calix[4]arene, and PDA derived polymers, etc. [10–13]. The above sensitive materials used for formaldehyde sensing take into account the important indicators of gas sensors, including excellent sensitivity, obvious selectivity, and rapid response speed.
Part per trillion level DMMP gas sensor based on calixarene modified organic thin film transistor
2022, Chemical Engineering JournalCitation Excerpt :Calixarenes are classified among macrocyclic compounds and have a unique 3D structure with a central cavity capable of interaction with many guest species [34]. Temel reported a novel calix[4]arene based QCM sensor which could achieve sensitive, selective and high performance-sensing of formaldehyde at room temperature [35]. We anticipate this modification could bring improvement for trace DMMP detection.