Aliphatic Aldehyde Detection and Adsorption by Nonporous Adaptive

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Aliphatic Aldehyde Detection and Adsorption by Nonporous Adaptive Pillar[4]arene[1]quinone Crystals with Vapochromic Behavior Errui Li, Kecheng Jie, Yujuan Zhou, Run Zhao, Bo Zhang, Qi Wang, Jiyong Liu, and Feihe Huang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b06396 • Publication Date (Web): 19 Jun 2018 Downloaded from http://pubs.acs.org on June 19, 2018

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ACS Applied Materials & Interfaces

Aliphatic Aldehyde Detection and Adsorption by Nonporous Adaptive Pillar[4]arene[1]quinone Crystals with Vapochromic Behavior Errui Li,† Kecheng Jie,† Yujuan Zhou,† Run Zhao,† Bo Zhang,‡ Qi Wang,‡ Jiyong Liu,† and Feihe Huang*,† †

State Key Laboratory of Chemical Engineering, Center for Chemistry of High-Performance &

Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China ‡

Department of Chemistry and Soft Matter Research Center, Zhejiang University, Hangzhou

310027, P. R. China. *Corresponding author. E-mail: [email protected]

ACS Paragon Plus Environment

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KEYWORDS: vapochromic behavior, gas adsorption, gas detection, pillararenes, nonporous adaptive crystals.

ABSTRACT: The detection and adsorption of volatile low-molecular-weight aliphatic aldehydes is of significance owing to their physical volatility, chemical toxicity and widespread applications in chemical industrial processes. Here nonporous adaptive pillar[4]arene[1]quinone (EtP4Q1) crystals with a vapochromic behavior are used for volatile aliphatic aldehyde uptake and sensing. When desolvated EtP4Q1 crystals (EtP4Q1) are exposed to aliphatic aldehydes with different carbon chain lengths, they quantitatively adsorb vapors of these aldehydes, accompanied by different color changes. Crystal structural analyses show that the structure of EtP4Q1 transforms from EtP4Q1 to the corresponding new structures after adsorption of these aldehydes, which leads to the different color changes. The selectivity of EtP4Q1 crystals which function as both sensors and adsorbents upon exposure to mixed aldehyde vapors is also explored. At last, it is demonstrated that EtP4Q1 crystals can be recycled many times without loss of performance.


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INTRODUCTION Aliphatic aldehydes are a class of toxic volatile organic compounds (VOC) which are undoubtedly harmful to environment safety and human health.1,2 As investigated, exposure to even low levels of aliphatic aldehydes damage the human respiratory system and in severe cases lead to cardiovascular disease.3,4 Owing to their widespread presence in industrial processes, chemical additives and incomplete combustions, the detection and adsorption of aliphatic aldehydes is of significance both in the chemical industry and in life.5 Up to now, a variety of methods have been used to detect volatile low-molecular-weight aldehydes, such as high resolution nuclear magnetic resonance (NMR) spectroscopy,6 quartz crystal microbalance (QCM),7 gas chromatography-mass spectrometry (GC-MS),8 high performance liquid chromatography (HPLC),9 electrochemical sensing,10 and so on. However, most of these gas/vapor detection methods cannot meet the requirement of operational simplicity and sensitivity for the detection of aldehyde vapors. Furthermore, the direct detection of aldehydes is complicated owing to their volatility, high polarity and chemical reactivity, as well as lack of chromophore or fluorophore. Thus, the discovery of sensitive and efficient sensors for volatile aldehydes is demanding. Another problem for the methods mentioned above is that none of them could be used to capture aldehyde vapors after detection. Thus, another challenge to be faced with is to find suitable aldehyde adsorbents. Considering the adsorption of aliphatic aldehydes, Barteau has investigated the adsorption of acetaldehyde and crotonaldehyde on the anatase and rutile polymorphs of TiO2 with Fourier transform infrared spectroscopy (FTIR).11 An and co-workers reported the heterogeneous atmospheric reactions of acetaldehyde, propanal, and butanal with NO2 onto silica (SiO2) clusters using a theoretical approach.12 Besides, Xu and co-workers


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introduced an electrospun polystyrene/graphene composite nanofiber film as a novel adsorbent for extraction of aldehydes in human exhaled breath condensates.13 However, these adsorbents can not detect adsorbates unless combined with specific testing equipments and have no selectivity for the simultaneous presence of several aliphatic aldehydes. Pillar[n]arenes have emerged as a new class of supramolecular macrocyclic hosts since 2008.14 Because of their unique pillar structure, simple chemical modification and abundant hostguest properties, they have been utilized in various supramolecular systems such as supramolecular amphiphiles, supramolecular polymers, macrocyclic amphiphiles, and so on.1518 Notably, some of these pillar[n]arene-based supramolecular systems work as sensors to detect toxic or hazardous species. For example, Wei and co-workers prepared a naphthalimidefunctionalized pillar[5]arene-based multiresponsive supramolecular polymer for fluorescence detection of cyanide, mercury, and cysteine.19 Yao and co-workers reported a Cu2+ specific metallogel for Cu2+ detection.20 However, these pillar[n]arene-based supramolecular systems still lack of the ability to efficiently capture hazardous species after detection. Recently, our group have reported that pillar[n]arene-based nonporous adaptive crystals could act as adsorbents to capture volatile species. The mechanism is totally different from porous materials with intrinsic porosity; the ―pores‖ in these nonporous crystals were only induced upon guest capture. For instance, we found that nonporous per-ethylated pillar[6]arene crystals capture iodine both in the air and in solution and separate styrene from ethylbenzene with high purity.21,22 Meanwhile, Ogoshi and co-workers reported that a pillar[5]arene showed a vapochromic behavior upon exposure to methanol or hexane.23 It is worth noting that a method or a material based on pillararenes or their derivatives that combines the functions of detection and adsorption of volatile aldehydes has never been reported to date. By combining the properties that


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pillar[n]arenes inherently have, we wonder whether pillararene derivatives can be tailored to not only detect but also adsorb volatile aldehydes. Here, we synthesized a pillar[4]arene[1]quinone (EtP4Q1) with four 1,4-diethoxybenzene units and one benzoquinone unit (Scheme 1a).24 We found that desolvated EtP4Q1 crystals (EtP4Q1) with a nonporous character visibly detect volatile aliphatic aldehydes such as acetaldehyde (C2), propionaldehyde (C3), butyraldehyde (C4), valeraldehyde (C5), and caproaldehyde (C6) (Scheme 1b) with a vapochromic behavior and meanwhile quantitatively adsorb all these aldehydes except formaldehyde (C1) into its cavity. Aliphatic aldehydes with different chain lengths led to different color changes of EtP4Q1 crystals. Crystal structure analyses showed that different color changes were generated from different crystal structure transformations after adsorption of different aldehydes, which influence the intermolecular charge-transfer of EtP4Q1 molecules in the solid state. Furthermore, EtP4Q1 crystals were reused many times without losing the detection and adsorption ability. RESULTS AND DISCUSSION EtP4Q1 was synthesized by partial oxidation of EtP5 with ammonium cerium nitrate in a mixture of tetrahydrofuran and water according to the literature and characterized by 1H NMR spectroscopy (Figure S1).24 As characterized by powder X-ray diffraction (PXRD), purified and desolvated EtP4Q1 powders were crystalline in the solid state (named as EtP4Q1, Figure S2). Same as nonporous adaptive pillar[n]arenes crystals reported previously,16 N2 sorption experiments showed these EtP4Q1 crystalline solids were not porous, indicating the dense packing of EtP4Q1 molecules in the crystalline state (Figure S3). Despite the nonporosity, we wondered whether EtP4Q1 crystals with deep red color could be used to detect aliphatic aldehydes. Interestingly, different color changes took place when


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activated crystals of EtP4Q1 were exposed to aliphatic aldehyde vapors, which was obviously a vapochromic behavior (Figure 1a). Aliphatic aldehydes containing four or less carbon atoms led to color changes of EtP4Q1 crystals from reddish brown to black, while aliphatic aldehydes with more than four carbon atoms made the color become bright red subsequently. However, the crystals did not show any color change when exposed to a formaldehyde vapor (Figure S5). These color changes were further measured by diffuse reflectance spectroscopy. The absorption bands in EtP4Q1 crystals increased in intensity after exposure to C2, C3 or C4, but decreased when exposed to C5 or C6. In order to study the detection efficiency of EtP4Q1, we monitored the time-dependence of the vapochromic behavior through diffuse reflectance spectroscopy. Here C3 and C6 were chosen as typical adsorbates. When EtP4Q1 crystals were exposed to C3, it took only 5 minutes to complete color change from reddish brown to black, while it took 40 minutes to complete the color change from reddish brown to bright red when exposed to C6 (Figure 1b and c). This is probably due to the lower boiling point of C3. The mechanism of the color change in EtP4Q1 crystals upon exposure to aliphatic aldehydes was then investigated. FTIR spectra showed a new peak appeared at 1715 cm1 for EtP4Q1 after exposure to aliphatic aldehyde vapors, representing the carbonyl stretching vibration absorption peak of aliphatic aldehydes (Figure S6). NMR spectra showed that new proton peaks related to aliphatic aldehydes appeared. By proton integration, we determined that one EtP4Q1 molecule captured nearly one aliphatic aldehyde molecule (Figure 1d). Moreover, the protons on the aliphatic aldehydes shifted upfield after they were adsorbed in EtP4Q1 crystals, indicating the complexations between aliphatic aldehyde molecules and the EtP4Q1 host (Figure S7S11). Thermogravimetric (TG) measurements were performed to investigate the adsorption capacity of EtP4Q1 crystals towards different aliphatic aldehydes. Compared with activated EtP4Q1


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crystals, aliphatic aldehydes-loaded EtP4Q1 crystals continued to lose weight at over 100 °C until the EtP4Q1 host began to decompose at about 350 °C (Figure S4 and S13). For the C3loaded EtP4Q1 (EtP4Q1-C3), there was a weight loss of 13.6 wt% of the crystals, which can be calculated as one C3 molecule per EtP4Q1 molecule. This agreed well with NMR experiments. For the C6-loaded EtP4Q1 (EtP4Q1-C6), there was a weight loss of 17.5 wt% of the crystals, which corresponds to one C6 molecule per EtP4Q1 molecule, also in good agreement with NMR experiments. These experiments indicated that nonporous EtP4Q1 crystals capture aldehyde vapors into the cavities of EtP4Q1 molecules. Structural analysis was carried out to investigate the color changes of EtP4Q1 crystals upon capture of aldehydes. The PXRD experiments showed that the original crystal structure of EtP4Q1 varied to some extent after adsorption of aldehydes (Figure 1e). It is noteworthy that the PXRD patterns of EtP4Q1 crystals after adsorption of C2, C3 and C4 were similar, while those after adsorption of C5 and C6 were similar, indicating that different chain lengths might be the major reason that leads to diffferent color changes. To accurately study the mechanism of EtP4Q1 as an aliphatic aldehyde adsorbent and different color changes of EtP4Q1 crystals after capturing aldehydes, dark brown single crystals of the EtP4Q1-C3 complex C3@EtP4Q1 were grown overnight by slow diffusion of methanol into a propionaldehyde solution of EtP4Q1. By the same method, we grew red single crystals of the EtP4Q1-C6 complex C6@EtP4Q1 and the EtP4Q1-C5 complex C5@EtP4Q1 (Figure S14S20). By X-ray crystallography, the resultant single crystal structures (Figure 2a and c) showed that one propionaldehyde or caproaldehyde molecule is stabilized in the cavity of EtP4Q1 by multiple CH/π interactions. Especially for C3@EtP4Q1, a double intermolecular hydrogen bond between the O atom of the C3 molecule located in the EtP4Q1 cavity and the H


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atom of the ethoxy group on the adjacent EtP4Q1 host was observed (Figure 2b), which further stabilizes the complex. The PXRD patterns of EtP4Q1-C3 and EtP4Q1-C6 crystals are in good agreement with the patterns simulated from their own single crystal structures (Figure S15 and S16), implying the structural transformation from EtP4Q1 to C3@EtP4Q1 or C6@EtP4Q1 after capturing C3 and C6 vapors. Depending on the different single crystal structures and PXRD patterns, the different colors attribute to differences in charge-transfer interactions between benzoquinone and 1,4-diethoxybenzene units. On one hand, in the crystal structure of C3@EtP4Q1, no intermolecular π-stacking between benzoquinone and 1,4-diethoxybenzene units on two adjacent host molecules was observed because the shape of EtP4Q1 is slightly distorted by drawing C3 into its cavity (Figure 2d). On the other hand, there were obvious intermolecular π-stacking and charge-transfer interactions between adjacent benzoquinone and 1,4-diethoxybenzene units in the crystal structure of C6@EtP4Q1 because of the highly symmetrical structure in the presence of C6 (Figure 2e), which is similar to C5@EtP4Q1. This structural difference leads to a difference in charge-transfer interactions between adjacent host molecules, which is the main reason for the aldehyde-length-dependent color change. With the aim of investigating selective uptake of aliphatic aldehyde vapors and detection of an aldehyde from a vapor mixture, solid-vapor sorption experiments were carried out for twocomponent aldehyde vapors. By exposing nonporous EtP4Q1 crystals to equimolar mixture of C3 and C6, the crystals showed color change from reddish brown to black at the first 5 hours but bright red after 10 hours and remained unchanged (Figure 3a). In situ PXRD experiments showed that EtP4Q1 was transformed to C3@EtP4Q1 after 5 hours but eventually turned to C6@EtP4Q1 (Figure 3b). To better understand this phenomenon, solid-vapor sorption experiments were carried out for two-component aldehyde vapors using C3@EtP4Q1 and


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C6@EtP4Q1 crystals, respectively. By exposing C3@EtP4Q1 crystals with black color to the C6 vapor, the color of crystals changed from black to bright red after 12 hours and remained unchanged, indicating the transformation from C3@EtP4Q1 to C6@EtP4Q1 (Figure S21). By exposing C6@EtP4Q1 crystals with bright red color to the C3 vapor, the color changed from bright red to black at the first 5 hours, but turned bright red eventually and remained unchanged when the black crystals were in air for 12 hours (Figure S22). The first color change was attributed to the surface adsorption of C3 molecules since the PXRD pattern of the crystals after the first color change was the same as that of EtP4Q1-C6. The second color change was due to the evaporation of surface-adsorbed C3 molecules since the PXRD pattern of the crystals did not change. The results of these color changes indicated that EtP4Q1 crystals preferentially adsorb C6 over C3, which is probably due to the more stable structure of C6@EtP4Q1 than that of C3@EtP4Q1. As can be analyzed from X-ray crystal structures, the presence of more CH/π interactions between caproaldehyde and EtP4Q1 in the C6@EtP4Q1 structure may contribute to a more stable structure than C3@EtP4Q1 with fewer CH/π interactions. The possibility that EtP4Q1 can not be used to detect formaldehyde is that formaldehyde has only two hydrogen atoms and not enough CH/ interactions can form between EtP4Q1 and formaldehyde. Density functional theory calculations were further performed to expound the binding energies of C3@EtP4Q1 and C6@EtP4Q1 (see details in the Supporting Information). The calculated results showed that the binding energy between EtP4Q1 and C3 was lower than that between EtP4Q1 and C6 (Table S2), confirming the more stable structure of C6@EtP4Q1 than C3@EtP4Q1. The reason why the color of EtP4Q1 crystals exposed to the mixture of C3 and C6 changed from reddish brown to black at the beginning of 5 hours and finally turned to bright red could be explained as follows: C3 with a smaller molecular weight has a lower boiling point,


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which makes it easier to be captured by EtP4Q1 crystals due to its higher concentration in the atmosphere, thus transforming EtP4Q1 to C3@EtP4Q1 at the beginning. However, the structure of C6@EtP4Q1 is more stable, and over time, C6 molecules diffuse into C3@EtP4Q1, displacing C3 molecules and transforming C3@EtP4Q1 into C6@EtP4Q1. Therefore, the crystal color eventually turned bright red. Another important parameter to evaluate is the sorption efficiency of adsorbents in cycling performance. To test this, C3@EtP4Q1 and C6@EtP4Q1 crystals were heated under vacuum at 100 °C for 48 h to obtain newly-formed desorbed EtP4Q1 crystals (EtP4Q1-C3-AF and EtP4Q1-C6-AF). We found that the color of EtP4Q1 crystals changed back from black and bright red to reddish brown. As characterized by PXRD, both of the newly-formed desolvated EtP4Q1 crystals were actually EtP4Q1, which were confirmed by FTIR and 1H NMR (Figure S24S29). Therefore, we demonstrated that the newly-formed EtP4Q1 crystals as the aliphatic aldehyde adsorbent and sensor can be recycled many times without degradation, relying on its structural thermal stability (Figure 4b). CONCLUSION In conclusion, we have demonstrated that EtP4Q1 crystals with a nonporous character can work as a new adsorbent and a visible vapochromic detector for volatile aliphatic aldehydes. When EtP4Q1 was exposed to aliphatic aldehydes containing different carbon chains lengths, it showed different color changes, which was resulted from different structures upon capture of the aldehydes. Nonporous EtP4Q1 crystals captured C3 and C6 into the cavity of EtP4Q1, transforming EtP4Q1 to C3@EtP4Q1 and C6@EtP4Q1, respectively. From the single crystal structures, we attribute the vapochromic behavior with different color changes to the difference of π-π stacking patterns between benzoquinone and 1,4-diethoxybenzene units in adjacent


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EtP4Q1 molecules, thus affecting their charge-transfer. What is more, EtP4Q1 crystals have the potential to preferentially adsorb C6 compared to C3 due to more CH/π interactions between caproaldehyde and the host. Significantly, compared to the other adsorbents, EtP4Q1 crystals have advantages such as simple synthesis, thermal stability and sensitivity. Moreover, they also work as absorbent for aldehyde vapors, thus making it unnecessary to seek other absorbent after detection of aldehyde vapors. At last, EtP4Q1 crystals can be regenerated by heating and recycled many times without loss of performance. The bi-functional EtP4Q1 crystals open up an arena for the application of pillararene-based nonporous adaptive crystals in sensor areas, especially the combination of different functions. EXPERIMENTAL SECTION All reagents were commercially available and used as supplied without further purification. EtP4Q1 was synthesized by partial oxidation of EtP5 with ammonium cerium nitrate in a mixture of tetrahydrofuran and water. For details, please refer to the Supporting Information.


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Scheme 1. (a) Synthetic route to pillar[4]arene[1]quinone EtP4Q1. (b) Chemical structures and cartoon representations of guests C2, C3, C4, C5 and C6.


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Figure 1. (a) Photographs showing color changes when 20 mg of EtP4Q1 crystals were exposed to different aliphatic aldehydes after 12 h. Time-dependent diffuse reflectance spectra of EtP4Q1 crystals exposed to propionaldehyde and caproaldehyde, respectively: (b) EtP4Q1-C3 and (c) EtP4Q1-C6. (d) Aliphatic aldehydes capture efficiency in EtP4Q1. (e) Corresponding powder X-ray diffraction patterns: (I) EtP4Q1; (II) EtP4Q1-C2; (III) EtP4Q1-C3; (IV) EtP4Q1-C4; (V) EtP4Q1-C5; (VI) EtP4Q1-C6.


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Figure 2. Views of single crystal structures: (a) C3@EtP4Q1; (b) two adjacent hostguest molecules of C3@EtP4Q1 along the c axis; (c) C6@EtP4Q1; (d) two adjacent host molecules of C3@EtP4Q1; (e) two adjacent host molecules of C6@EtP4Q1. Hydrogen bond parameters: H···O distance (Å), C···O distance (Å), C—H···O angle (deg): a, 2.670, 3.625, 164.95; b, 2.670, 3.625, 164.95.


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Figure 3. (a) Photographs showing color changes when EtP4Q1α is exposed to an equimolar mixture of C3 and C6. (b) Powder X-ray diffraction patterns: (I) EtP4Q1-C3; (II) EtP4Q1α after adsorption of the mixture for 5 h; (III) EtP4Q1α after adsorption of the mixture for 15 h; (IV) EtP4Q1-C6.


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Figure 4. (a) Schematic representation of EtP4Q1 as the adsorbent for aliphatic aldehyde vapors capture and recycling of EtP4Q1. (b) Aliphatic aldehyde capture efficiency in EtP4Q1 after the same material is recycled 5 times.


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ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website. Synthesis rout and process, 1H NMR spectrum, XRD patterns, DRS, FTIR spectra, TGA, and N2 adsorption-desorption isotherms. AUTHOR INFORMATION Corresponding Author * F. Huang. E-mail: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21434005, 91527301), the Fundamental Research Funds for the Central Universities, and the Open Project of State Key Laboratory of Supramolecular Structure and Materials (sklssm201611). REFERENCES (1) Kargbo, D. M.; Wilhelm, R. G.; Campbell, D. J. Natural Gas Plays in the Marcellus Shale: Challenges and Potential Opportunities. Environ. Sci. Technol. 2010, 44, 56795684.


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(2) Bamberger, M.; Oswald, R. E. Impacts of Gas Drilling on Human and Animal Health. New Solut. 2012, 22, 5177. (3) Feron, V. J.; Arts, J. H.; Kuper, C. F.; Slootweg, P. J.; Woutersen, R. A. Health Risks Associated with Inhaled Nasal Toxicants. Crit. Rev. Toxicol. 2001, 31, 313347. (4) Saladino, A. J.; Willey, J. C.; Lechner, J. F.; Grafstrom, R. C.; LaVeck, M.; Harris, C. C. Effects of Formaldehyde, Acetaldehyde, Benzoyl Peroxide, and Hydrogen Peroxide on Cultured Normal Human Bronchial Epithelial Cells. Cancer Res. 1985, 45, 25222526. (5) Calestani, D.; Mosca, R.; Zanichelli, M.; Villani, M.; Zappettini, A. Aldehyde Detection by ZnO Tetrapod-Based Gas Sensors. J. Mater. Chem. 2011, 1553, 1553215536. (6) Dugo, G.; Rotondo, A.; Mallamace, D.; Cicero, N.; Salvo, A.; Rotondo, E.; Corsaro, C. Enhanced Detection of Aldehydes in Extra-Virgin Olive Oil by Means of Band Selective NMR Spectroscopy. Physica A. 2015, 420, 258264. (7) Liu, C.; Wyszynski, B.; Yatabe, R.; Hayashi, K.; Toko, K. Molecularly Imprinted Sol-GelBased QCM Sensor Arrays for the Detection and Recognition of Volatile Aldehydes. Sensors 2017, 17, 382396. (8) Serrano, M.; Silva, M.; Gallego, M. Development of an Environment-Friendly Microextraction Method for the Determination of Aliphatic and Aromatic Aldehydes in Water. Anal. Chim. Acta. 2013, 784, 7784.


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(9) Li, Y.; Yi, F.; Zheng, Y.; Wang, Y.; Ye, J.; Chu, Q. Hollow-Fiber Liquid-Phase Microextraction Coupled with Miniature Capillary Electrophoresis for the Trace Analysis of Four Aliphatic Aldehydes in Water Samples. J. Sep. Sci. 2015, 38, 28732879. (10) Obermeier, J.; Trefz, P.; Wex, K.; Sabel, B.; Schubert, J. K.; Miekisch, W. Electrochemical Sensor System for Breath Analysis of Aldehydes, CO and NO. J. Breath Res. 2015, 9, 016008. (11) Rekoske, J. E.; Barteau, M. A. Competition between Acetaldehyde and Crotonaldehyde during Adsorption and Reaction on Anatase and Rutile Titanium Dioxide. Langmuir 1999, 15, 20612070. (12) Ji, Y.; Wang, H.; Chen, J.; Li, G.; An, T.; Zhao, X. Can Silica Particles Reduce Air Pollution by Facilitating the Reactions of Aliphatic Aldehyde and NO2? J. Phys. Chem. A. 2015, 119, 1137611383. (13) Huang, J.; Deng, H.; Song, D.; Xu, H. Electrospun Polystyrene/Graphene Nanofiber Film as a Novel Adsorbent of Thin Film Microextraction for Extraction of Aldehydes in Human Exhaled Breath Condensates. Anal. Chim. Acta. 2015, 878, 102108. (14) Ogoshi, T.; Kanai, S.; Fujinami, S.; Yamagishi, T.; Nakamoto, Y. para-Bridged Symmetrical Pillar[5]arenes: Their Lewis Acid Catalyzed Synthesis and HostGuest Property. J. Am. Chem. Soc. 2008, 130, 50225023. (15) Huang, X.; Du, X. Pillar[6]arene-Valved Mesoporous Silica Nanovehicles for Multiresponsive Controlled Release. ACS Appl. Mater. Interfaces 2014, 6, 2043020436.


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(16) Jie, K.; Zhou, Y.; Li, E.; Zhao, R.; Liu, M.; Huang, F. Linear Positional Isomer Sorting in Nonporous Adaptive Crystals of a Pillar[5]arene. J. Am. Chem. Soc. 2018, 140, 31903193. (17) Cheng, H.-B.; Li, Z.; Huang, Y.-D.; Liu, L.; and Wu, H.-C. Pillararene-Based Aggregation-Induced-Emission-Active Supramolecular System for Simultaneous Detection and Removal of Mercury(II) in Water. ACS Appl. Mater. Interfaces 2017, 9, 1188911894. (18) Ji, X.; Xia, D.; Yan, X.; Wang, H.; Huang, F. Supramolecular Polymer Materials Based on Crown Ether and Pillararene Host-Guest Recognition Motifs. Acta Polym. Sin. 2017, 1, 918. (19) Lin, Q.; Zhong, K.-P.; Zhu, J.-H.; Ding, L.; Su, J.-X.; Yao, H.; Wei, T.-B.; Zhang, Y.-M. Iodine Controlled Pillar[5]arene-Based Multiresponsive Supramolecular Polymer for Fluorescence Detection of Cyanide, Mercury, and Cysteine. Macromolecules 2017, 50, 78637871. (20) Jie, K.; Zhou, Y.; Shi, B.; Yao, Y. A Cu2+ Specific Metallohydrogel: Preparation, Multiresponsiveness and Pillar[5]arene-Induced Morphology Transformation. Chem. Commun. 2015, 51, 84618164. (21) Jie, K.; Zhou, Y.; Li, E.; Zhao, R.; Li, Z.; Huang, F. Reversible Iodine Capture by NonPorous Pillar[6]arene Crystals. J. Am. Chem. Soc. 2017, 139, 1532015323. (22) Jie, K.; Liu, M.; Zhou, Y.; Little, M. A.; Bonakala, S.; Chong, S. Y.; Stephenson, A.; Chen, L.; Huang, F.; Cooper, A. I. Styrene Purification by Guest-Induced Restructuring of Pillar[6]arene. J. Am. Chem. Soc. 2017, 139, 29082911.


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(23) Ogoshi, T.; Shimada, Y.; Sakata, Y.; Akine, S.; Yamagishi, T. Alkane-Shape-Selective Vapochromic Behavior Based on Crystal-State Host–Guest Complexation of Pillar[5]arene Containing One Benzoquinone Unit. J. Am. Chem. Soc. 2017, 139, 56645667. (24) Han, C.; Zhang, Z.; Yu, G.; Huang, F. Syntheses of a Pillar[4]arene[1]quinone and a Difunctionalized Pillar[5]arene by Partial Oxidation. Chem. Commun. 2012, 48, 98769878.


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Aliphatic Aldehyde Detection and Adsorption by Nonporous Adaptive

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