CO2 capture by multivalent amino-functionalized calix[4]arenes: self-assembly, absorption, and QCM detection studies.

The reactivity of CO(2) with polyamino substrates based on calix[4]arenes and on a difunctional, noncyclic model has been studied. All the compounds react with CO(2) in chloroform to form ammonium carbamate salts. However, the number, topology, and conformational features of the amino-functionalized arms present on the multivalent scaffold have a remarkable influence on the reaction efficiency and on the product composition. Tetraaminocalix[4]arenes 1-3 rapidly and efficiently react with 2 equiv of CO(2), yielding highly stable hydrogen-bonded dimers formed by the self-assembly of two bis-ammonium bis-carbamate intramolecular salts. 1,3-Diaminocalix[4]arene 4 absorbs 1 mol of CO(2), affording less stable zwitterionic ammonium carbamates. Gemini compound 5 reacts with CO(2) in a 1:1 stoichiometry, forming hydrogen-bonded dimers of ammonium carbamate derivatives of moderate stability. For upper rim 1,3-diaminocalix[4]arene 6, in addition to the labile intramolecular salt, the presence of a self-assembled polymer was also detected. These systems were fully characterized in solution by (1)H and (13)C NMR spectroscopy, whereas the corresponding gas-solid reactions were further investigated by QCM measurements. Interestingly, the high affinity and reversibility of CO(2) uptake shown by 1,3-diamino calix[4]arene 4 enabled us to attain a promising QCM device for carbon dioxide sensing.

[1]  B. Smit,et al.  Carbon dioxide capture: prospects for new materials. , 2010, Angewandte Chemie.

[2]  F. Fotiadu,et al.  CO2 binding by dynamic combinatorial chemistry: an environmental selection. , 2010, Journal of the American Chemical Society.

[3]  E. Dalcanale,et al.  Vacuum-Evaporated Cavitand Sensors: Dissecting Specific from Nonspecific Interactions in Ethanol Detection , 2008 .

[4]  G. Donofrio,et al.  Macrocyclic nonviral vectors: high cell transfection efficiency and low toxicity in a lower rim guanidinium calix[4]arene. , 2008, Organic letters.

[5]  A. Macchioni,et al.  Determining accurate molecular sizes in solution through NMR diffusion spectroscopy. , 2008, Chemical Society reviews.

[6]  D. Vos,et al.  Green synthesis of carbamates from CO2, amines and alcohols , 2008 .

[7]  D. Rudkevich,et al.  Using carbon dioxide and calix[4]arenes to separate sodium. , 2007, Chemical communications.

[8]  Jeffery T. Davis,et al.  Membrane-active calixarenes: toward 'gating' transmembrane anion transport , 2007 .

[9]  F. Sansone,et al.  Calixarene-based multivalent ligands. , 2007, Chemical Society reviews.

[10]  D. Rudkevich,et al.  Separations using carbon dioxide. , 2007, Journal of the American Chemical Society.

[11]  D. Rudkevich,et al.  Supramolecular structures from lysine peptides and carbon dioxide. , 2006, The Journal of organic chemistry.

[12]  Heng Xu,et al.  Controlling capture and release of guests from cross-linked supramolecular polymers. , 2005, Organic letters.

[13]  F. Sansone,et al.  Calixarene‐Based Picolinamide Extractants for Selective An/Ln Separation from Radioactive Waste , 2005 .

[14]  Yoram Cohen,et al.  Diffusion NMR spectroscopy in supramolecular and combinatorial chemistry: an old parameter--new insights. , 2005, Angewandte Chemie.

[15]  M. Horiguchi,et al.  Studies on the solvent dependence of the carbamic acid formation from ω-(1-naphthyl)alkylamines and carbon dioxide , 2005 .

[16]  Heng Xu,et al.  CO2 in supramolecular chemistry: preparation of switchable supramolecular polymers. , 2004, Chemistry.

[17]  D. Rudkevich,et al.  Exploring reversible reactions between CO2 and amines , 2003 .

[18]  Fabio Marchetti,et al.  Converting carbon dioxide into carbamato derivatives. , 2003, Chemical reviews.

[19]  Richard G. Weiss,et al.  Detection of Pre-Sol Aggregation and Carbon Dioxide Scrambling in Alkylammonium Alkylcarbamate Gelators by Nuclear Magnetic Resonance† , 2003 .

[20]  Piero Baglioni,et al.  Synthesis and characterization of gels from polyallylamine and carbon dioxide as gellant. , 2003, Journal of the American Chemical Society.

[21]  Michele Aresta,et al.  Reaction of silylalkylmono- and silylalkyldi-amines with carbon dioxide: evidence of formation of inter- and intra-molecular ammonium carbamates and their conversion into organic carbamates of industrial interest under carbon dioxide catalysis , 2002 .

[22]  Richard G. Weiss,et al.  Chemically Reversible Organogels via “Latent” Gelators. Aliphatic Amines with Carbon Dioxide and Their Ammonium Carbamates† , 2002 .

[23]  A. K. Biswas,et al.  Removal of carbon dioxide by absorption in mixed amines: modelling of absorption in aqueous MDEA/MEA and AMP/MEA solutions , 2001 .

[24]  R. Weiss,et al.  Chemically reversible organogels: aliphatic amines as "latent" gelators with carbon dioxide. , 2001, Journal of the American Chemical Society.

[25]  J. E. Lyons,et al.  Catalysis research of relevance to carbon management: progress, challenges, and opportunities. , 2001, Chemical reviews.

[26]  K. W. Jung,et al.  Efficient carbamate synthesis via a three-component coupling of an amine, CO2, and alkyl halides in the presence of Cs2CO3 and tetrabutylammonium iodide. , 2001, The Journal of organic chemistry.

[27]  Karsten Henkel,et al.  Increased sensor sensitivities obtained by polymer-coated quartz microbalances , 1999 .

[28]  J. Lakowicz,et al.  Sensing of carbon dioxide by a decrease in photoinduced electron transfer quenching. , 1999, Analytical biochemistry.

[29]  A. Marra,et al.  Synthesis of Calix[4]arenylvinylene and Calix[4]arenylphenylene Oligomers by Stille and Suzuki Cross-Coupling Reactions , 1998 .

[30]  F. Sansone,et al.  Synthesis and Properties of O‐Glycosyl Calix[4]Arenes (Calixsugars) , 1997 .

[31]  L. Valli,et al.  Porphyrin dimers linked by a conjugated alkyne bridge : Novel moieties for the growth of Langmuir-Blodgett films and their applications in gas sensors , 1997 .

[32]  T. Mallouk,et al.  Molecular Design of Intercalation-Based Sensors. 2. Sensing of Carbon Dioxide in Functionalized Thin Films of Copper Octanediylbis(phosphonate) , 1997 .

[33]  W. Göpel,et al.  Mass sensitive detection of carbon dioxide by amino group-functionalized polymers , 1996 .

[34]  Ji-Ho Yoon,et al.  Solubility of Carbon Dioxide in Monoethanolamine + Ethylene Glycol + Water and Monoethanolamine + Poly(ethylene glycol) + Water , 1996 .

[35]  Yi Pan,et al.  Carbon Dioxide as a Phosgene Replacement: Synthesis and Mechanistic Studies of Urethanes from Amines, CO2, and Alkyl Chlorides , 1995 .

[36]  R. Ungaro,et al.  Calix[4]arenes Blocked in a Rigid Cone Conformation by Selective Functionalization at the Lower Rim , 1995 .

[37]  D. Reinhoudt,et al.  Synthesis, Complexation, and Membrane Transport Studies of 1,3-Alternate Calix[4]arene-crown-6 Conformers: A New Class of Cesium Selective Ionophores , 1995 .

[38]  E. Dalcanale,et al.  Selective detection of organic compounds by means of cavitand-coated QCM transducers , 1995 .

[39]  W. Göpel,et al.  Reliable CO2 sensors with silicon-based polymers on quartz microbalance transducers , 1994 .

[40]  Michele Aresta,et al.  Role of the macrocyclic polyether in the synthesis of N-alkylcarbamate esters from primary amines, CO2 and alkyl halides in the presence of crown-ethers. , 1992 .

[41]  J. Alauzun,et al.  Reversible Covalent Chemistry of CO2: An Opportunity for Nano-Structured Hybrid Organic–Inorganic Materials , 2008 .

[42]  C. Hunter,et al.  Fast, reversible optical sensing of NO2 using 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine assemblies , 2001 .

[43]  S. E. Matthews,et al.  Calix[4]arenes with CMPO functions at the narrow rim. Synthesis and extraction properties , 1999 .

[44]  D. Reinhoudt,et al.  Upper-rim urea-derivatized calix[4]arenes as neutral receptors for monocarboxylate anions , 1996 .

[45]  Udo Weimar,et al.  Soluble phthalocyanines for the detection of organic solvents: thin film structures with quartz microbalance and capacitance transducers , 1995 .

[46]  S. Shinkai,et al.  NMR spectroscopic and X-ray crystallographic studies of calix[4]arene·Ag+complexes. Influence of bound Ag+ on C2v–C2v interconversion in cone-calix[4]arenes , 1994 .