Metallocalix[4]arene Polymers for Gravimetric Detection of N-Nitrosodialkylamines.

N-Nitrosamines are found in food, drugs, air, water, and soil. They pose a significant risk to human health because of their carcinogenicity; consequently, materials that can be used to selectively and sensitively detect nitrosamines are needed. In this work, we designed and synthesized two polymers bearing calix[4]arene or 4-tert-butylcalix[4]arene tungsten-imido complexes (PCalixH and PCalixtBu) as N-nitrosodimethylamine (NDMA) receptors. The interaction between metallocalix[4]arene monomers/polymers and NDMA was confirmed by 1H NMR and IR spectroscopy. Single-crystal X-ray analysis further revealed that the host-guest interaction is based on binding of the terminal oxygen of NDMA to tungsten within the calixarene cavity. Gravimetric detection of NDMA was performed on a quartz crystal microbalance (QCM) in air. Both polymers show responses to NDMA, with PCalixtBu exhibiting a low theoretical limit of detection of 5 ppb for NDMA. The sensor also shows high selectivity toward NDMA and moderate humidity tolerance. This work provides a sensitive sensor for detection of NDMA and also offers a class of new, selective, and efficient NDMA receptors for the future design of NDMA sensors and NDMA extraction materials.

[1]  T. Swager,et al.  An Organic Chemist's Guide to N-Nitrosamines: Their Structure, Reactivity, and Role as Contaminants. , 2021, The Journal of organic chemistry.

[2]  J. Essigmann,et al.  Chemiresistive Carbon Nanotube Sensors for N-Nitrosodialkylamines. , 2019, ACS sensors.

[3]  Feihe Huang,et al.  Supramolecular‐Macrocycle‐Based Crystalline Organic Materials , 2019, Advanced materials.

[4]  Jong Seung Kim,et al.  Revisiting Fluorescent Calixarenes: From Molecular Sensors to Smart Materials. , 2019, Chemical reviews.

[5]  R. Montero-Montoya,et al.  Volatile Organic Compounds in Air: Sources, Distribution, Exposure and Associated Illnesses in Children , 2018, Annals of global health.

[6]  T. Hofstetter,et al.  Formation of N-Nitrosodimethylamine during Chloramination of Secondary and Tertiary Amines: Role of Molecular Oxygen and Radical Intermediates. , 2017, Environmental science & technology.

[7]  N. Voelcker,et al.  Electrochemical detection of N‐nitrosodimethylamine using a molecular imprinted polymer , 2016 .

[8]  T. Swager,et al.  Functionalized Metallated Cavitands via Imidation and Late-Stage Elaboration. , 2015, European journal of organic chemistry.

[9]  T. Swager,et al.  Detection and differentiation of neutral organic compounds by 19F NMR with a tungsten calix[4]arene imido complex. , 2013, Journal of the American Chemical Society.

[10]  P. Anzenbacher,et al.  Supramolecular sensor for cancer-associated nitrosamines. , 2012, Journal of the American Chemical Society.

[11]  W. Mitch,et al.  Halonitroalkanes, halonitriles, haloamides, and N-nitrosamines: a critical review of nitrogenous disinfection byproduct formation pathways. , 2012, Environmental Science and Technology.

[12]  Bernd Becker,et al.  A survey of the 2006–2009 quartz crystal microbalance biosensor literature , 2011, Journal of molecular recognition : JMR.

[13]  J. Croué,et al.  Chloramination of nitrogenous contaminants (pharmaceuticals and pesticides): NDMA and halogenated DBPs formation. , 2011, Water research.

[14]  Jong Seung Kim,et al.  Recognition of amino acids by functionalized calixarenes. , 2011, Chemical Society reviews.

[15]  D. Powell,et al.  Five- and six-coordinate adducts of nitrosamines with ferric porphyrins: structural models for the Type II interactions of nitrosamines with ferric cytochrome P450. , 2010, Inorganic chemistry.

[16]  Matthew A Cooper,et al.  A survey of the 2001 to 2005 quartz crystal microbalance biosensor literature: applications of acoustic physics to the analysis of biomolecular interactions , 2007, Journal of molecular recognition : JMR.

[17]  R. L. Valentine,et al.  Modeling the formation of N-nitrosodimethylamine (NDMA) from the reaction of natural organic matter (NOM) with monochloramine. , 2006, Environmental science & technology.

[18]  W. Mitch,et al.  Nitrosamine formation pathway revisited: the importance of chloramine speciation and dissolved oxygen. , 2006, Environmental science & technology.

[19]  Stephen S. Hecht,et al.  Tobacco carcinogens, their biomarkers and tobacco-induced cancer , 2003, Nature Reviews Cancer.

[20]  M. Meyyappan,et al.  Carbon Nanotube Sensors for Gas and Organic Vapor Detection , 2003 .

[21]  A. West,et al.  Interactions of organic nitroso compounds with metals. , 2002, Chemical reviews.

[22]  David L Sedlak,et al.  Formation of N-nitrosodimethylamine (NDMA) from dimethylamine during chlorination. , 2002, Environmental science & technology.

[23]  G. B. Richter‐Addo,et al.  Synthesis, Characterization, and Molecular Structures of Diethylnitrosamine Metalloporphyrin Complexes of Iron, Ruthenium, and Osmium. , 1998, Inorganic chemistry.

[24]  D. Diamond.  Calixarene-based sensing agents , 1996 .

[25]  P. Knekt,et al.  Dietary intakes of nitrate, nitrite and NDMA in the Finnish Mobile Clinic Health Examination Survey. , 1996, Food additives and contaminants.

[26]  J. Cauvin,et al.  Analysis of N-nitrosamines by high-performance liquid chromatography with post-column photohydrolysis and colorimetric detection. , 1996, Journal of chromatography. A.

[27]  G. B. Richter‐Addo,et al.  THE FIRST METALLOPORPHYRIN NITROSAMINE COMPLEX : BIS(DIETHYLNITROSAMINE)(MESO-TETRAPHENYLPORPHYRINATO)IRON(III) PERCHLORATE , 1995 .

[28]  L. A. Currie,et al.  Nomenclature in evaluation of analytical methods including detection and quantification capabilities (IUPAC Recommendations 1995) , 1995 .

[29]  Stephen K. Brown,et al.  Concentrations of Volatile Organic Compounds in Indoor Air – A Review , 1994 .

[30]  H. Yamazaki,et al.  Cytochrome P450 2E1 and 2A6 enzymes as major catalysts for metabolic activation of N-nitrosodialkylamines and tobacco-related nitrosamines in human liver microsomes. , 1992, Carcinogenesis.

[31]  C. Rizzoli,et al.  Mononuclear tungsten(VI) calix[4]arene complexes , 1991 .

[32]  A R Tricker,et al.  Carcinogenic N-nitrosamines in the diet: occurrence, formation, mechanisms and carcinogenic potential. , 1991, Mutation research.

[33]  M. Ward,et al.  In Situ Interfacial Mass Detection with Piezoelectric Transducers , 1990, Science.

[34]  C. D. Gutsche.  The Calixarenes , 1984, Structural Chemistry.

[35]  B. Spiegelhalder,et al.  Occupational nitrosamine exposure. 1. Rubber and tyre industry. , 1983, Carcinogenesis.

[36]  B. Krebs,et al.  Kristallstruktur des N‐Nitrosodimethylamins , 1975 .