Sample records for calixarenes

  1. Applications of calixarenes in cancer chemotherapy: facts and perspectives

    Directory of Open Access Journals (Sweden)

    Yousaf A


    Full Text Available Ali Yousaf,1 Shafida Abd Hamid,1 Noraslinda M Bunnori,1 AA Ishola2 1Kulliyyah of Science, 2Kulliyyah of Medicine, International Islamic University Malaysia, Bandar Indera Mahkota, Malaysia Abstract: Research on the therapeutic applications of calixarene derivatives is an emerging area of interest. The anticancer activity of various functionalized calixarenes has been reported by several research groups. Due to their superior geometric shape, calixarenes can accommodate drug molecules by forming inclusion complexes. Controlled release of anticancer drugs by calixarenes might help in targeted chemotherapy. This review summarizes the anticancer potential of the calixarenes and their drug loading properties. The potential use of calixarenes in chemoradiotherapy is also highlighted in brief. Keywords: cancer, chemotherapy, calixarenes

  2. A bis-calixarene from olefin metathesis

    Directory of Open Access Journals (Sweden)

    Shimelis T. Hailu


    Full Text Available A ring-closing olefin metathesis reaction of tetrakis(allyloxycalix[4]arene gave the bis calixarene, (15E,40E,60E-65,74-bis(prop-2-en-1-yloxy-13,18,38,43,58,63-hexaoxadodecacyclo[,36.111,45.151,55.05,57.07,12.019,24.026,64.032,37.044,49.168,72]tetraheptaconta-1,3,5(57,7,9,11,15,19(24,20,22,26,28,30(64,32,34,36,40,44(49,45,47,51,53,55(65,60,68,70,72(74-heptacosaene, C74H68O8. It is a cage formed from two calix[4]arene units joined by butenyl groups at three of the O atoms on the narrow rim. The fourth O atom on each calixarene unit is joined with an allyl group. Each of the calix[4]arene units has a flattened cone conformation in which the allyloxy-substituted aryl group and the opposite aryl group are close together and almost parallel [dihedral angle between planes = 1.09 (11°], and the other two aryl groups are splayed outward [dihedral angle between planes = 79.53 (11°]. No guest molecule (e.g. solvent was observed within the cage. The alkene C atoms of one of the links between the calixarene moieties are disordered over two orientations with occupancies of 0.533 (9 and 0.467 (9.

  3. A bis-calixarene from olefin metathesis (United States)

    Hailu, Shimelis T.; Butcher, Ray J.; Hudrlik, Paul F.; Hudrlik, Anne M.


    A ring-closing olefin metathesis reaction of tetra­kis­(all­yl­oxy)calix[4]arene gave the bis­ calixarene, (15E,40E,60E)-65,74-bis­(prop-2-en-1-yl­oxy)-13,18,38,43,58,63-hexa­oxado­deca­cyclo­[,36.111,45.151,55.05,57.07,12.019,24.026,64.032,37.044,49.168,72]tetra­hepta­conta-1,3,5(57),7,9,11,15,19(24),20,22,26,28,30(64),32,34,36,40,44(49),45,47,51,53,55(65),60,68,70,72(74)-hepta­cosa­ene, C74H68O8. It is a cage formed from two calix[4]arene units joined by butenyl groups at three of the O atoms on the narrow rim. The fourth O atom on each calixarene unit is joined with an allyl group. Each of the calix[4]arene units has a flattened cone conformation in which the all­yloxy-substituted aryl group and the opposite aryl group are close together and almost parallel [dihedral angle between planes = 1.09 (11)°], and the other two aryl groups are splayed outward [dihedral angle between planes = 79.53 (11)°]. No guest mol­ecule (e.g. solvent) was observed within the cage. The alkene C atoms of one of the links between the calixarene moieties are disordered over two orientations with occupancies of 0.533 (9) and 0.467 (9). PMID:22719604

  4. A bis-calixarene from olefin metathesis. (United States)

    Hailu, Shimelis T; Butcher, Ray J; Hudrlik, Paul F; Hudrlik, Anne M


    A ring-closing olefin metathesis reaction of tetra-kis-(all-yl-oxy)calix[4]arene gave the bis- calixarene, (15E,40E,60E)-65,74-bis-(prop-2-en-1-yl-oxy)-13,18,38,43,58,63-hexa-oxado-deca-cyclo-[,36).1(11,45).1(51,55).0(5,57).0(7,12).0(19,24).0(26,64).0(32,37).0(44,49).1(68,72)]tetra-hepta-conta-1,3,5(57),7,9,11,15,19(24),20,22,26,28,30(64),32,34,36,40,44(49),45,47,51,53,55(65),60,68,70,72(74)-hepta-cosa-ene, C(74)H(68)O(8). It is a cage formed from two calix[4]arene units joined by butenyl groups at three of the O atoms on the narrow rim. The fourth O atom on each calixarene unit is joined with an allyl group. Each of the calix[4]arene units has a flattened cone conformation in which the all-yloxy-substituted aryl group and the opposite aryl group are close together and almost parallel [dihedral angle between planes = 1.09 (11)°], and the other two aryl groups are splayed outward [dihedral angle between planes = 79.53 (11)°]. No guest mol-ecule (e.g. solvent) was observed within the cage. The alkene C atoms of one of the links between the calixarene moieties are disordered over two orientations with occupancies of 0.533 (9) and 0.467 (9).

  5. Calixarene-entrapped nanoemulsion for uranium extraction from contaminated solutions. (United States)

    Spagnul, Aurélie; Bouvier-Capely, Céline; Phan, Guillaume; Rebière, François; Fattal, Elias


    Accidental cutaneous contamination by actinides such as uranium occurring to nuclear power plant workers can lead to their dissemination in other tissues and induce severe damages. Until now, no specific emergency treatment for such contamination has been developed. The aim of the present work was to formulate a tricarboxylic calix[6]arene molecule, known to exhibit good affinity and selectivity for complexing uranium, within a topical delivery system for the treatment of skin contamination. Since calixarene was shown to reduce oil/water interfacial tension, we have designed an oil-in-water nanoemulsion, taking advantage of the small droplet size offering a high contact surface with the contaminated aqueous medium. Characterization of the calixarene nanoemulsion was performed by determination of the oily droplet size, zeta potential and pH, measured as a function of the calixarene concentration. The obtained results have confirmed the surface localization of calixarene molecules being potentially available to extract uranyl ions from an aqueous contaminated solution. In a preliminary experiments, the calixarene nanoemulsion was used for the removal of free uranium from an aqueous contaminated solution. Results showed that the calixarene nanoemulsion extracted up to 80 +/- 5% of uranium, which demonstrates the potential interest of this delivery system for uranium skin decontamination.

  6. Bridging of Calixarenes with N,N'-Bis(Chloroacetyl)Propylenediamine

    Institute of Scientific and Technical Information of China (English)

    LI Jun; WANG Wei; GONG shu-ling; CHEN Yuan-yin


    A new bridging reagent, N,N′-bis(chloroacetyl)propylenediamine was used to explore the relative activity and bridging pattern of p-tert-butylcalix[4]arene, p-tert-butylcalix[6]arene and butylcalix[8]arene. It was found that the bridging reaction is selectively, at least, preferably at 1,3-position for p-tert-butylcalix[4]arene and p-tert-butylcalix[6]arene, 1,5-position for p-tert-butylcalix[8]arene. Taking the yield of bridged calixarene as a comparsion standard, the activity decreases with the increasing of the number of phenolic units in calixarene.

  7. New Chiral Calixarene Derivatives: Syntheses and Their Chiral Recognition Toward Amino Acids by UV-Vis Spectroscopy

    Institute of Scientific and Technical Information of China (English)


    Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognition properties of these host compounds towards L- and D-threonine were studied by UV-Vis spectroscopy. The results indicated that calixarene derivatives 5 and 8 exhibited good chiral recognition capabilities toward L- or D-threonine. Although calixarene derivative 10 had no evident chiral recognition ability, the supramolecules of calixarene derivative 10 with L- or D-threonine showed a hypochromic effect or hyperchromic effect respectively. Therefore, calixarene derivative 10 might serve as a good chiral UV-indicator.

  8. Application of Calixarenes as Macrocyclic Ligands for Uranium(VI: A Review

    Directory of Open Access Journals (Sweden)

    Katarzyna Kiegiel


    Full Text Available Calixarenes represent a well-known family of macrocyclic molecules with broad range of potential applications in chemical, analytical, and engineering materials fields. This paper covers the use of calixarenes as complexing agents for uranium(VI. The high effectiveness of calix[6]arenes in comparison to other calixarenes in uranium(VI separation process is also presented. Processes such as liquid-liquid extraction (LLE, liquid membrane (LM separation, and ion exchange are considered as potential fields for application of calixarenes as useful agents for binding UO22+ for effective separation from aqueous solutions containing other metal components.

  9. Caesium extraction by calixarene molecules: Some aspects of extraction kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Simon, N.; Tournois, B.; Volle, G


    In the framework of the environment Code (2000 studies were developed to recover long-lived fission products (F.P.) from acidic highly radioactive effluents issuing the reprocessing of spent fuels, to destroy them by transmutation or to encapsulate them into specific matrices. Efforts had been directed towards caesium, particularly {sup 135}Cs, which is one of the most harmful fission products because of its long half life (more than 2.10{sup 6} years) and its mobility in repository. The flow-sheet will be included in the general scheme of long-lived radionuclide partitioning. It was decided to define a process based on liquid-liquid extraction. Crown-calixarenes molecules were chosen for process development. To refine the flowsheet diagram, it is necessary to know the rate constants of the implied chemical reactions involved in the extraction. This paper describes the first determination of rate constant in the Cs extraction with crown calixarenes. (authors)

  10. Calix 2007:9th International Conference on Calixarene Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Jeffery Davis


    The DOE funds helped support an International Conference, Calix 2007, whose focus was on Supramolecular Chemistry. The conference was held at the University of Maryland from August 6-9, 2007 (Figure 1). The conference website is at This biannual conference had previously been held in the Czech Republic (2005), Canada (2003), Netherlands (2001), Australia (1999), Italy (1997), USA (Fort Worth, 1995) Japan (1993) and Germany (1991). Calixarenes are cup-shaped compounds that are a major part of Supramolecular Chemistry, for which Cram, Lehn and Pederson were awarded a Nobel Prize 20 years ago. Calixarene chemistry has expanded greatly in the last 2 decades, as these compounds are used in synthetic and mechanistic chemistry, separations science, materials science, nanoscience and biological chemistry. The organizing committee was quite happy that Calix 2007 encompassed the broad scope and interdisciplinary nature of the field. Our goal was to bring together leading scientists interested in calixarenes, molecular recognition, nanoscience and supramolecular chemistry. We believe that new research directions and collaborations resulted from an exchange of ideas between conferees. This grant from the DOE was crucial toward achieving that goal, as the funds helped cover some of the registration and accommodations costs for the speakers.


    Institute of Scientific and Technical Information of China (English)

    Zhi-quan Shen


    The studies of our group on the catalytic activities of rare earth calixarene complexes in polymer syntheses are reviewed. Rare earth calixarene complexes are effect catalysts for the polymerizations of butadiene, isoprene, ethylene,styrene, propylene oxide, styrene oxide, trimethylene carbonate and 2,2-dimethyl-trimethylene carbonate.

  12. Quick and efficient extraction of uranium from a contaminated solution by a calixarene nanoemulsion. (United States)

    Spagnul, Aurélie; Bouvier-Capely, Céline; Adam, Marc; Phan, Guillaume; Rebière, François; Fattal, Elias


    This work aims to evaluate the efficiency of a calixarene emulsion for uranium extraction from a contaminated solution prior to apply such a delivery system to uranium skin decontamination. For this purpose, various experimental parameters that can influence the efficiency of the calixarene emulsion on uranium extraction were determined. The results show that the calixarene nanoemulsion effect can be observed after a very short time of contact with uranium-contaminated solution (5 min) and that it is still efficient in case of small volumes of contaminated solution. The pH of the contaminated solution was found to be the most important parameter affecting the calixarene nanoemulsion efficiency with a dramatic reduction of the uranium extraction rate in case of acidification of the contaminated medium. This lack of efficiency can be overcome by buffering the nanoemulsion continuous phase. The obtained results reveal that the calixarene nanoemulsion could represent a promising system for the emergency treatment of uranium cutaneous contamination.

  13. Calixarenes: Versatile molecules as molecular sensors for ion recognition study

    Indian Academy of Sciences (India)

    Subrata Patra; Debdeep Maity; Ravi Gunupuru; Pragati Agnihotri; Parimal Paul


    This article presents a brief account on designing of calixarene-based molecular sensor for recognition of various metal ions and anions and also different analytical techniques to monitor the recognition event. This review focuses only on calix[4]arene derivatives, in which mainly the lower rim is modified incorporating either crown moiety to make calix-crown hybrid ionophore to encapsulate metal ions or some fluoregenic inorganic and organic moieties to use it as signalling unit. In order to investigate effect of conformation of the calixarene unit and steric crowding on ion selectivity, designing of these molecules have been made using both the cone and 1,3-alternate conformations of the calixarene unit and also incorporating bulky tert-butyl group in few cases to impose controlled steric crowding. Among various ions, here focuses are mainly on biologically and commercially important alkali metal ion such as K+, toxic metal ions such as Hg2+, Pb2+, Cd2+, important transition metal ion such as Cu2+ and toxic anion like F−. The techniques used to monitor the recognition event and also to determine binding constants with strongly interacting ions are fluorescence, UV-vis and 1H NMR spectroscopy. Most of the ionophores reported in this review have been characterized crystallographically, however no structural information (except one case) are incorporated in this article, as it will occupy space without significant enhancement of chemistry part. Different factors such as size of the ionophore cavity, size of metal ion, coordination sites/donor atoms, steric crowding and solvents, which determine selectivity have been discussed. Response of ion recognition process to different analytical techniques is another interesting factor discussed in this article.

  14. Hyperbranched calixarenes: synthesis and applications as fluorescent probes. (United States)

    Kim, Jong Seung; Lee, Su Yeon; Yoon, Juyoung; Vicens, Jacques


    This feature article is a timely review of a portion of the authors' work concerning the chemistry of dendrimers and subsequent related fluorescent probes. The design of supramolecular systems provides an original approach to nanoscience and nanochemistry. The construction of well-defined functional architectures of nanometric size represents a way of performing programmed engineering of nanomaterials. Among the nanomaterials, dendrimers are set apart, and very recently a large number of works have been devoted to the elaboration of molecular sensors. These two aspects will be developed in this article from the authors' experience with calixarenes.

  15. Synthesis of calixarenes and their extraction performance for ester catechins

    Institute of Scientific and Technical Information of China (English)


    A series of extractants (tert-butylcalix[6]arene, tert-butylcalix[8]arene and octeacetate of tert-butylcalix[8]arene) were synthesized, and their structures were identified by IR and 1H-NMR. The distribution behavior of ester catechins monomer in the aqueous and chloroform two-phase system containing one of calixarene was studied. The influences of different extractants,concentration of tert-butylcalix[8]arene and extraction temperature on the partition coefficients and the separation factors were investigated. The experiment results show that tert-butylcalix[8]arene is the best extractant that forms a more stable supramolecular compound with gallocatechin gallate (GCG) than with epigallocathechin gallate (EGCG) or epicatechin gallate (ECG). When the concentration ofp-tert-butylcalix[8]arene is 3.79 mmol/L, the extraction temperature is 4 ℃C, the partition coefficients of KGG cG, KECG,KEGG cG are 0.987, 0.629, 0.449, the separation factors ofα1 and α2 are 1.450 and 1.596, respectively. The important factors influencing the extraction properties of calixarene are discovered to be its cavity size and hydrogen bonding.

  16. Synthesis, solid and solution studies of paraquat dichloride calixarene complexes. Molecular modelling

    Energy Technology Data Exchange (ETDEWEB)

    Garcia S, I.; Ramirez, F. M., E-mail: flor.ramirez@inin.gob.m [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)


    The interaction of the herbicide paraquat dichloride (P Q, substrate) with p-tert-butylcalix arenas (L, receptor) was investigated in both the solution and solid states. The isolated paraquat calixarene complexes were characterised by UV-visible, {sup 1}H NMR, ESI-Ms, Luminescence and IR spectroscopies and elemental analysis. The stoichiometry of complexes 1 and 2 was 1:1 (1 herbicide: 1 calixarene) and both revealed a biexponential luminescence decay with lifetimes depending on the size and the conformational particularity of the calixarenes. Molecular modelling suggested that both calixarenes interact with the herbicide through cation-{pi} interaction. P Q in included in the p-tert butylcalix a rene cavity, a situation favoured by its pinched conformation in polar solvent while it is partially included in the p-tert butylcalix a rene cavity because of its in-out cone conformation. The theoretical results, in particular using Mopac procedures, were in agreement with the experimental findings. (Author)

  17. Lanthanides and actinides extraction by calixarenes containing CMPO groups; Extraction des lanthanides et des actinides au moyen de calixarenes portant des groupements CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Garcia Carrera, A


    In the framework of the French program SPIN concerning the radioactive waste management, researches are performed to develop processes allowing the separation of long-lived radioisotopes in order to their transmutation or their specific conditioning. These studies deal with the extraction and the separation of trivalent lanthanides and actinides in acid solution. Many systems ''calixarene-diluent-aqueous phase'' are examined by extraction liquid-liquid and membrane transport. The extraction efficiency and the selectivity of the synthesized calixarene-CMPO and of the CMPO are compared with these cations, as the nitric acid extraction by these molecules. (A.L.B.)

  18. Fabrication, characterization and gas sensing properties of gold nanoparticle and calixarene multilayers

    Indian Academy of Sciences (India)



    Calixarenes are a group of materials that are widely used for gas sensing studies because of their simple synthesis, conformational flexibility, binding group tunability, variability in their cavity sizes and improved selectivity to different gas molecules. In recent years it has been shown that incorporation of gold nanoparticles (AuNPs) into organic layers further enhances their gas sensing performance. The present study reports on the fabrication of thin films of calixarene and AuNPs using Langmuir–Schaefer (LS) methods. The gas sensing properties of the produced films are investigated on exposure to saturated vapours of volatile organic compounds (VOCs) using surface plasmon resonance as an optical detection technique. Multilayers comprising films of AuNPs and calixarene have been investigated to evaluate the effect of AuNPs on the films sensing performances. It has been demonstrated that the hybrid layers exhibited improved sensing performance in terms of the degree of their response.

  19. A calixarene-based ion-selective electrode for thallium(I) detection

    Energy Technology Data Exchange (ETDEWEB)

    Chester, Ryan [Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia 6845 (Australia); Sohail, Manzar [Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast, Locked Bag 4, Maroochydore DC, Queensland 4556 (Australia); Ogden, Mark I.; Mocerino, Mauro [Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia 6845 (Australia); Pretsch, Ernö [ETH Zürich, Institute of Biogeochemistry and Pollutant Dynamics (IBP), Universitätstrasse 16, CH-8092, Zürich (Switzerland); De Marco, Roland, E-mail: [Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box U1987, Perth, Western Australia 6845 (Australia); Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast, Locked Bag 4, Maroochydore DC, Queensland 4556 (Australia)


    Highlights: • Tuning of metal binding cavities in thallium(I) calixarene ionophores. • Novel calixarene-based ionophores with improved selectivity for thallium(I). • Sandwich membrane characterization of thallium(I) binding in novel calixarenes. • Improved selectivity and sensitivity with novel thallium(I) calixarene ionophores. • Solid contact ion-selective electrodes for novel thallium(I) calixarene ionophores. - Abstract: Three new calixarene Tl{sup +} ionophores have been utilized in Tl{sup +} ion-selective electrodes (ISEs) yielding Nernstian response in the concentration range of 10{sup −2}–10{sup −6} M TlNO{sub 3} with a non-optimized filling solution in a conventional liquid contact ISE configuration. The complex formation constants (log β{sub IL}) for two of the calixarene derivatives with thallium(I) (i.e. 6.44 and 5.85) were measured using the sandwich membrane technique, with the other ionophore immeasurable due to eventual precipitation of the ionophore during these long-term experiments. Furthermore, the unbiased selectivity coefficients for these ionophores displayed excellent selectivity against Zn{sup 2+}, Ca{sup 2+}, Ba{sup 2+}, Cu{sup 2+}, Cd{sup 2+} and Al{sup 3+} with moderate selectivity against Pb{sup 2+}, Li{sup +}, Na{sup +}, H{sup +}, K{sup +}, NH{sub 4}{sup +} and Cs{sup +}, noting that silver was the only significant interferent with these calixarene-based ionophores. When optimizing the filling solution in a liquid contact ISE, it was possible to achieve a lower limit of detection of approximately 8 nM according to the IUPAC definition. Last, the new ionophores were also evaluated in four solid-contact (SC) designs leading to Nernstian response, with the best response noted with a SC electrode utilizing a gold substrate, a poly(3-octylthiophene) (POT) ion-to-electron transducer and a poly(methyl methacrylate)–poly(decyl methacrylate) (PMMA–PDMA) co-polymer membrane. This electrode exhibited a slope of 58.4 mV decade

  20. Anionic Calixarene-Capped Silver Nanoparticles Show Species-Dependent Binding to Serum Albumins

    Directory of Open Access Journals (Sweden)

    Anthony W. Coleman


    Full Text Available The anionic calixarenes para-sulphonatocalix[4]arene and 1,3-di-Ophosphonatocalix[ 4]arene, have been used to cap silver nanoparticles. The binding of these functional particles with regard to various serum albumins (bovine serum albumin, human serum albumin, porcine serum albumin and sheep serum albumin has been studied by variable temperature fluorescence spectroscopy. The quenching of the fluorescence of the proteins was shown to vary as a function of the anionic calixarene capping molecule and also as a function of the origin of the serum albumin. It is thus possible to discriminate between the different species.

  1. Anionic calixarene-capped silver nanoparticles show species-dependent binding to serum albumins. (United States)

    Tauran, Yannick; Brioude, Arnaud; Kim, Beomjoon; Perret, Florent; Coleman, Anthony W


    The anionic calixarenes para-sulphonatocalix[4]arene and 1,3-di-O-phosphonatocalix[ 4]arene, have been used to cap silver nanoparticles. The binding of these functional particles with regard to various serum albumins (bovine serum albumin, human serum albumin, porcine serum albumin and sheep serum albumin) has been studied by variable temperature fluorescence spectroscopy. The quenching of the fluorescence of the proteins was shown to vary as a function of the anionic calixarene capping molecule and also as a function of the origin of the serum albumin. It is thus possible to discriminate between the different species.

  2. Study of the alkaline cations complexation by photo-isomerizable calixarenes; Etude de la complexation de cations alcalins par des calixarenes photoisomerisables

    Energy Technology Data Exchange (ETDEWEB)

    Reynier, N.


    The first step to reduce the volume and the toxicity of radioactive waste coming from the spent fuel reprocessing is to separate long life radioisotopes from others ones with a shorter period. The aim of this study is to show that the control of the two phenomenons, complexation of the cation by the calixarenes and its de-complexation, can be envisaged by the introduction on the molecule of a chromophore group, azo benzene, able to modify the complexing site structure of the calixarenes with an isomerization trans-cis induced by ultraviolet radiation, and isomerization cis-trans thermally induced by a visible radiation. (N.C.). 112 refs., 78 figs., 23 tabs.

  3. Calixarene-based molecular capsule from olefin metathesis

    Directory of Open Access Journals (Sweden)

    Shimelis T. Hailu


    Full Text Available The reaction of tetrakis(allyloxycalix[4]arene with the first-generation Grubbs catalyst, followed by catalytic hydrogenation, gave the novel bis-calixarene 15,20,46,51,64,69,74,79-octaoxatridecacyclo[,28.113,53.122,44.09,14.021,26.038,70.040,45.052,57.059,63.07,80.032,73]octaconta-1(63,3,5,7(80,9(14,10,12,21,23,25,28(73,29,31,34,36,38(70,40,42,44,52,54,56,59,61-tetracosaene benzene monosolvate, C72H72O8·C6H6. The structure consists of two calix[4]arene units connected by four-carbon chains at each of the four O atoms on their narrow rims, to form a cage. Each of the calix[4]arene units has a flattened cone conformation in which two of the opposite aryl groups are closer together and nearly parallel [dihedral angle between planes = 7.35 (16°], and the other two aryl groups are splayed outward [dihedral angle between planes = 72.20 (8°]. While the cavity contains no solvent or other guest molecule, there is benzene solvent molecule in the lattice. Two of the alkyl linking arms were disordered over two conformations with occupancies of 0.582 (3/0.418 (3 and 0.33 (4/0.467 (4. They were constrained to have similar metrical and thermal parameters.

  4. Synthesis of Two Blue-light - emitting Complexes with Schiff Base Calixarene as the Ligand

    Institute of Scientific and Technical Information of China (English)


    Two new blue luminescent zinc and beryllium complexes with Schiff base calixarene derivative as the ligand were prepared. Their luminescent properties were determined, which indicated that they had strong blue fluorescent properties. They also had good solubility and film formation. These new complexes can be used as blue organic electroluminescent materials (OELMs) in organic electroluminescent devices.

  5. Synthesis and Complexation Studies of Calix[4]crown Telomers Intermolecularly Bridged with Calixarene Segments

    Institute of Scientific and Technical Information of China (English)

    LI Haibing; TIAN Demei; CHEN Yuanyin; GAO Zhinong


    Three derivatived calix[4]crowns were condensed with calixarene segments: 2,6-bis(bromomethyl)-4-methyl-anisole (BBA) to afford their telomers TCA[4] in rational yields. The binding sites may complex metal ions or amino acids selectively. The telomers shows different metal ions selectivity in comparison with their monomers, which suggests that calixarene segment bridges play an important role in ion-binding. The liquid-liquid extraction experiment showed that telomer TCA[4]-Ⅲ was excellent receptor for zwitterionic a-amino acids and soft cations Ag+ and Pb2+. The extraction percentage of tryptophan and histidine was as high as 87.9% and 91.5%, respec-tively.

  6. High extraction ability of 1,3-dialkynyl calixarene towards mercury(Ⅱ) ion

    Institute of Scientific and Technical Information of China (English)

    Lin Bo Gong; Shu Ling Gong; Qin Zheng; Xiong Li; Yuan Yin Chen


    The reaction of 1,3-dipropyn-2-yloxycalix[4]arene with mercury(Ⅱ) acetate could give mercury-containing alkynyl calixarene polymer. The extraction behavior of 1,3-dipropyn-2-yl-oxycalix[4]arene towards mercury(H) ion was examined. When the mole ratio of Hg2+/calixarene was 1∶1, the extractive percent can reach to 99.1%, and the extraction capacity was up to 431 mg/g. It could also decrease the Hg2+ concentration from 5 to 0.85 mg/L, which was only 17% of the national standard of effluent and satisfied the national standard of drinking water. The extraction process included chemical reaction.

  7. The Liquid-Liquid Extraction of Toxic Metals (Cd, Hg and Pb by Calixarenes

    Directory of Open Access Journals (Sweden)

    D. Max Roundhill


    Full Text Available Toxic metals (Cd, Hg and Pb are mostly present in the environment due to natural phenomenon and human activities as well. Exposure of these non-essential elements in the environment causes severe effects. They are known to cause problems in humans as well as in aquatic life. In this work, we demonstrate various studies regarding liquid-liquid extraction of selected ions with different functionalized calixarenes. This review article briefly discusses several molecular designs of calixarenes for divalent ion (Cd2+, Hg2+ and Pb2+ recognition; as well as the relationship between structure and selectivity of the macrocycles is elaborated. The article does not, however, attempt to cover all of the different approaches to these toxic metal ions extraction.

  8. Catalytic consequences of the structural environment and electronics of Ti in grafted Ti-calixarenes

    Energy Technology Data Exchange (ETDEWEB)

    Notestein, Justin M.; Katz, Alexander; Iglesia, Enrique [University of California, Berkeley, CA (United States). Dept. of Chemical Engineering; Andrini, Leandro R.; Requejo, Felix G. [Universidad Nacional de La Plata (Argentina). Inst. de Fisica; Consejo Nacional de Investigaciones Cientificas y Tecnicas, Buenos Aires (Argentina). Facultad de Ciencias Exactas. Dept. de Fisica; Kalchenko, Vitaly I. [National Academy of Sciences (Ukraine). Inst. of Organic Chemistry


    Calixarene-metal complexes provide the opportunity for fundamental studies to correlate basic characteristics and properties of molecules and atomic species. In particular because grafted Ti-calixarenes provide Ti centers with varying electron density and coordination but maintain accessible sites (active centers) with uniform structures and unrestricted access to reactants, they allow for a systematic approach to relating oxidation reactivity to Ti 3d occupancy, a descriptor of Lewis acid strength, and Ti coordination. Thus, the relationship between activity, geometry and concepts of electronics in catalysis can be revisited and clarified due to the well-defined nature of these Ti sites, allied to the chemical and local sensitivity of X-ray absorption techniques. (author)

  9. Calixarenes and cations: a time-lapse photography of the big-bang. (United States)

    Casnati, Alessandro


    The outstanding cation complexation properties emerging from the pioneering studies on calixarene ligands during a five-year period in the early 1980s triggered a big-bang burst of publications on such macrocycles that is still lasting at a distance of more than 30 years. A time-lapse photography of this timeframe is proposed which allows the readers to pinpoint the contributions of the different research groups.

  10. The Design and Development of a Regenerative Separatory Column Using Calixarenes as a Polymeric Backbone for the Purification of Water from Urine (United States)

    Polk, M.


    The objective of this research project is to design calixarenes, cup-shaped molecules, with the specific binding sites to the sodium chloride and nitrogen containing components of urine, such as urea and uric acid, in urine. The following partition of the research accomplishes this objective: (1) functionalization of calixarene, (2) development of a calixarene based medium for the separatory process, (3) design of the column regeneration protocol. Work was also accomplished in the area of temperature sensitive paint (TSP). Research was undertaken to design a TSP with insulating propertites. An important part of this research project is to discover the thermal conductivity of polymers for TSP.

  11. Protein-Sized Bright Fluorogenic Nanoparticles Based on Cross-Linked Calixarene Micelles with Cyanine Corona. (United States)

    Shulov, Ievgen; Rodik, Roman V; Arntz, Youri; Reisch, Andreas; Kalchenko, Vitaly I; Klymchenko, Andrey S


    The key challenge in the field of fluorescent nanoparticles (NPs) for biological applications is to achieve superior brightness for sizes equivalent to single proteins (3-7 nm). We propose a concept of shell-cross-linked fluorescent micelles, in which PEGylated cyanine 3 and 5 bis-azides form a covalently attached corona on micelles of amphiphilic calixarene bearing four alkyne groups. The fluorescence quantum yield of the obtained monodisperse NPs, with a size of 7 nm, is a function of viscosity and reached up to 15 % in glycerol. In the on-state they are circa 2-fold brighter than quantum dots (QD-585), which makes them the smallest PEGylated organic NPs of this high brightness. FRET between cyanine 3 and 5 cross-linkers at the surface of NPs suggests their integrity in physiological media, organic solvents, and living cells, in which the NPs rapidly internalize, showing excellent imaging contrast. Calixarene micelles with a cyanine corona constitute a new platform for the development of protein-sized ultrabright fluorescent NPs.

  12. New composites based on poly(3-trimethylsilyltricyclononene-7) and organic nature fillers (calixarenes & cyclodextrins) (United States)

    Chapala, Pavel P.; Bermeshev, Maxim V.; Starannikova, Ludmila E.; Gavrilova, Natalie N.; Shantarovich, Victor P.; Filatova, Marina P.; Krut'ko, Ekaterina B.; Yampolskii, Yurii P.; Finkelshtein, Eugene Sh.


    Herein we describe new materials for membrane gas separation process with improved selectivities towards different pairs of gases. Organic nature fillers (modified calix[4]arenes, calix[8]arenes and modified α-, β-, γ-cyclodextrins) were used as additives to poly(trimethylsilyltricyclononene-7) (PTCNSi1)in order to study correlations between structure of the filling agent and gas transport parameters of the composite membranes. It was shown a positive influence of calixarenes and cyclodextrins as additives on permselectivity of the membranes. For instance, selectivity towards H2/CH4 gas pair increased almost in 2.4 times when calix[4]arene with Et- and tert-Bu- group was introduced into polymeric matrix. Detailed study of the PTCNSi1 adsorbtion/desortion data is presented. The obtained composites were characterized by TEM, WAXD, PALS and BET analysis.

  13. Study of the simultaneous complexation of a cation and of an anion using functionalized calixarenes; Etude de la complexation simultanee d'un cation et d'un anion par des calixarenes fonctionnalises

    Energy Technology Data Exchange (ETDEWEB)

    Moli, Ch. [CEA Cadarache, Dept. d' Etudes des Dechets, DED, 13 - Saint Paul lez Durance (France)]|[Universite Louis Pasteur, 67 - Strasbourg (France)


    The chemical reprocessing of irradiated nuclear fuels leads to the production of high-level radioactive liquid wastes which contain long-lived toxic radioelements. In the framework of the long-term management of these wastes, important research work is carried out for the separation of these radioelements for their further transmutation or immobilization inside specific matrices. These radioelements are present in acid solutions of fission products in the form of cations (cesium), anions (technetium, selenium) and molecules (iodine). Crown calixarenes have been successfully used for the extraction of cesium thanks to their exceptional selectivities. This work is mainly based on the use of the chelating properties of calixarenes for the extraction of anionic radioelements. Calixarenes functionalized by amino-carbon chains have been selected. The synthesis of amine calix[4]arenes and calix[6]arenes is described and their extractive and ionophoretic properties with respect to radioelements are shown using aqueous selective separation techniques like the liquid-liquid extraction and the supported liquid membrane transport. Technetium and selenium are extracted by amine calixarenes from a 10{sup -2} M aqueous solution of nitric acid. At this acidity, no selenium transport is observed, while technetium transport is efficient: the solution is quasi-totally decontaminated in 6 hours. Molecular iodine is efficiently extracted with a simple organic diluent, the 1,2-nitro-phenyl-hexyl-ether, from a strongly concentrated aqueous solution of nitric acid (HNO{sub 3} = 3 M). The transport of iodine becomes faster and more efficient when its concentration in the solution is higher. (J.S.)

  14. 亚甲基修饰杯芳烃%Brief Introduction of Functionalized Calixarenes on Methylene Bridge

    Institute of Scientific and Technical Information of China (English)

    董慧民; 郑浩; 冶保献


      从三方面介绍了杯芳烃亚甲基修饰的研究概况,主要有引入杂原子、取代亚甲基的氢和亚甲基存在不饱和键等形式。这些修饰改变了杯芳烃的构象等性质,扩展了杯芳烃的分子、离子识别等功能。%  The functionalization of methylene group of calixarenes is introduced briefly. The introduction of heteroatoms as bridging atoms, the substitution of hydrogen atom, and unsaturated bond on the methylene bridge of calixarenes would offer additional opportunities to modify their properties, affinity and selectivity for binding ions or molecules.

  15. A simple and rapid method for calixarene-based selective extraction of bioactive molecules from natural products. (United States)

    Segneanu, Adina-Elena; Damian, Daniel; Hulka, Iosif; Grozescu, Ioan; Salifoglou, Athanasios


    Natural products derived from medicinal plants have gained an important role in drug discovery due to their complex and abundant composition of secondary metabolites, with their structurally unique molecular components bearing a significant number of stereo-centers exhibiting high specificity linked to biological activity. Usually, the extraction process of natural products involves various techniques targeting separation of a specific class of compounds from a highly complex matrix. Aiding the process entails the use of well-defined and selective molecular extractants with distinctly configured structural attributes. Calixarenes conceivably belong to that class of molecules. They have been studied intensely over the years in an effort to develop new and highly selective receptors for biomolecules. These macrocycles, which display remarkable structural architectures and properties, could help usher a new approach in the efficient separation of specific classes of compounds from complex matrices in natural products. A simple and rapid such extraction method is presented herein, based on host-guest interaction(s) between a calixarene synthetic receptor, 4-tert-butyl-calix[6]arene, and natural biomolecular targets (amino acids and peptides) from Helleborus purpurascens and Viscum album. Advanced physicochemical methods (including GC-MS and chip-based nanoESI-MS analysis) suggest that the molecular structure and specifically the calixarene cavity size are closely linked to the nature of compounds separated. Incorporation of biomolecules and modification of the macrocyclic architecture during separation were probed and confirmed by scanning electronic microscopy and atomic force microscopy. The collective results project calixarene as a promising molecular extractant candidate, facilitating the selective separation of amino acids and peptides from natural products.

  16. Sequence-specific DNA interactions with calixarene-based langmuir monolayers. (United States)

    Rullaud, Vanessa; Moridi, Negar; Shahgaldian, Patrick


    The interactions of an amphiphilic calixarene, namely p-guanidino-dodecyloxy-calix[4]arene, 1, self-assembled as Langmuir monolayers, with short double stranded DNA, were investigated by surface pressure-area (π-A) isotherms, surface ellipsometry and Brewster angle microscopy (BAM). Three DNA 30mers were used as models, poly(AT), poly(GC) and a random DNA sequence with 50% of G:C base pairs. The interactions of these model DNA duplexes with 1-based Langmuir monolayers were studied by measuring compression isotherms using increasing DNA concentrations (10(-6), 10(-5), 10(-4), and 5 × 10(-4) g L(-1)) in the aqueous subphase. The isotherms of 1 showed an expansion of the monolayer with, interestingly, significant differences depending on the duplex DNA sequence studied. Indeed, the interactions of 1-based monolayers with poly(AT) led to an expansion of the monolayer that was significantly more pronounced that for monolayers on subphases of poly(GC) and the random DNA sequence. The structure and thickness of 1-based Langmuir monolayers were investigated by BAM and surface ellipsometry that showed differences in thickness and structure between a monolayer formed on pure water or on a DNA subphase, with here again relevant dissimilarities depending on the DNA composition.

  17. Novel urea-linked cinchona-calixarene hybrid-type receptors for efficient chromatographic enantiomer separation of carbamate-protected cyclic amino acids. (United States)

    Krawinkler, Karl Heinz; Maier, Norbert M; Sajovic, Elisabeth; Lindner, Wolfgang


    Two novel diastereomeric cinchona-calixarene hybrid-type receptors (SOs) were synthesized by inter-linking 9-amino(9-deoxy)-quinine (AQN)/9-amino(9-deoxy)-epiquinine (eAQN) and a calix[4]arene scaffold via an urea functional unit. Silica-supported chiral stationary phases (CSPs) derived from these SOs revealed, for N-protected amino acids, complementary chiral recognition profiles in terms of elution order and substrate specificity. The AQN-derived CSP showed narrow-scoped enantioselectivity for open-chained amino acids bearing pi-acidic aromatic protecting groups, preferentially binding the (S)-enantiomers. In contrast, the eAQN congener exhibited broad chiral recognition capacity for open-chained as well as cyclic amino acids, and preferential binding of the (R)-enantiomers. Exceedingly strong retention due to nonenantioselective hydrophobic analyte-calixarene interactions observed with hydro-organic mobile phases could be largely suppressed with organic mobile phases containing small amounts of acetic acid as acidic modifier. With the eAQN-calixarene hybrid-type CSP particularly high levels of enantioselectivity could be achieved for tert-butoxycarbonyl (Boc)-, benzyloxycarbonyl (Z)- and fluorenylmethoxycarbonyl (Fmoc)-protected cyclic amino acids using chloroform as mobile phase, e.g. an enantioselectivty factor alpha >5.0 for Boc-proline. Increasing amounts of acetic acid compromised enantioselectivity, indicating the crucial contributions of hydrogen bonding to chiral recognition. Comparison of the performance characteristics of the urea-linked eAQN-calixarene hybrid-type CSP with those of structurally closely related mutants provided evidence for the active involvement of the urea and calixarene units in the chiral recognition process. The urea linker motif was shown to contribute to analyte binding via multiple hydrogen bonding interactions, while the calixarene module is believed to support stereodiscrimination by enhancing the shape complementarity of the

  18. Langmuir monolayers of an inclusion complex formed by a new calixarene derivative and fullerene. (United States)

    González-Delgado, Antonio M; Giner-Casares, Juan J; Brezesinski, Gerald; Regnouf-de-Vains, Jean-Bernard; Camacho, Luis


    The design of new molecules with directed interactions to functional molecules as complementary building blocks is one of the main goals of supramolecular chemistry. A new p-tert-butylcalix[6]arene monosubstituted derivative bearing only one alkyl chain with an acid group (C6A3C) has been synthesized. The C6A3C has been successfully used for building Langmuir monolayers at the air-water interface. The C6A3C molecule adopts a flatlike orientation with respect to the air-water interface. The molecular structure gives the molecule amphiphilic character, while allowing the control of both the dissociation degree and the molecular conformation at the air-water interface. The C63AC has been combined with pristine fullerene (C60) to form the supramolecular complex C6A3C:C60 in 2:1 molar ratio (CFC). The CFC complex retains the ability of C6A3C to form Langmuir monolayers at the air/water interface. The interfacial molecular arrangement of the CFC complex has been convincingly described by in situ UV-vis reflection spectroscopy and synchrotron X-ray reflectivity measurements. Computer simulations complement the experimental data, confirming a perpendicular orientation of the calixarene units of CFC with respect to the air-water interface. This orientation is stabilized by the formation of intermolecular H-bonds. The interfacial monolayer of the CFC supramolecular complex is proposed as a useful model for the well-defined self-assembly of recognition and functional building blocks.

  19. Calixarene-based mol­ecular capsule from olefin metathesis (United States)

    Hailu, Shimelis T.; Butcher, Ray J.; Hudrlik, Paul F.; Hudrlik, Anne M.


    The reaction of tetra­kis­(all­yloxy)calix[4]arene with the first-generation Grubbs catalyst, followed by catalytic hydrogenation, gave the novel bis-calixarene 15,20,46,51,64,69,74,79-octa­oxatridecacyclo[,28.113,53.122,44.09,14.021,26.038,70.040,45.052,57.059,63.07,80.032,73]octa­conta-1(63),3,5,7(80),9(14),10,12,21,23,25,28(73),29,31,34,36,38(70),40,42,44,52,54,56,59,61-tetra­cosa­ene benzene monosolvate, C72H72O8·C6H6. The structure consists of two calix[4]arene units connected by four-carbon chains at each of the four O atoms on their narrow rims, to form a cage. Each of the calix[4]arene units has a flattened cone conformation in which two of the opposite aryl groups are closer together and nearly parallel [dihedral angle between planes = 7.35 (16)°], and the other two aryl groups are splayed outward [dihedral angle between planes = 72.20 (8)°]. While the cavity contains no solvent or other guest mol­ecule, there is benzene solvent mol­ecule in the lattice. Two of the alkyl linking arms were disordered over two conformations with occupancies of 0.582 (3)/0.418 (3) and 0.33 (4)/0.467 (4). They were constrained to have similar metrical and thermal parameters. PMID:24046590

  20. Compared in vivo efficiency of nanoemulsions unloaded and loaded with calixarene and soapy water in the treatment of superficial wounds contaminated by uranium. (United States)

    Grivès, Sophie; Phan, Guillaume; Bouvier-Capely, Céline; Suhard, David; Rebière, François; Agarande, Michelle; Fattal, Elias


    No emergency decontamination treatment is currently available in the case of radiological skin contamination by uranium compounds. First responders in the workplace or during an industrial nuclear accident must be able to treat internal contamination through skin. For this purpose, a calixarene nanoemulsion was developed for the treatment of intact skin or superficial wounds contaminated by uranium, and the decontamination efficiency of this nanoemulsion was investigated in vitro and ex vivo. The present work addresses the in vivo decontamination efficiency of this nanoemulsion, using a rat model. This efficiency is compared to the radio-decontaminant soapy water currently used in France (Trait rouge(®)) in the workplace. The results showed that both calixarene-loaded nanoemulsion and non-loaded nanoemulsion allowed a significant decontamination efficiency compared to the treatment with soapy water. Early application of the nanoemulsions on contaminated excoriated rat skin allowed decreasing the uranium content by around 85% in femurs, 95% in kidneys and 93% in urines. For skin wounded by microneedles, mimicking wounds by microstings, nanoemulsions allowed approximately a 94% decrease in the uranium retention in kidneys. However, specific chelation of uranium by calixarene molecules within the nanoemulsion was not statistically significant, probably because of the limited calixarene-to-uranium molar ratio in these experiment conditions. Moreover, these studies showed that the soapy water treatment potentiates the transcutaneous passage of uranium, thus making it bioavailable, in particular when the skin is superficially wounded.

  1. Chromatographic analysis of some drugs employed in erectile dysfunction therapy: qualitative and quantitative studies using calixarene stationary phase. (United States)

    Hashem, Hisham; Ibrahim, Adel Ehab; Elhenawee, Magda


    In this study, the effect of change in chromatographic process variables on the retention behavior of four drugs employed in erectile dysfunction therapy on a calixarene stationary phase is described. Three of these drugs are known to treat erectile dysfunction, namely, sildenafil citrate, tadalafil, and apomorphine hydrochloride, and one drug that is used as opioid analgesic, tramadol hydrochloride, which is quiet widely misused to treat premature ejaculation. The results indicate the importance of considering the structure and pKa values of drugs to be separated along with mobile phase composition. A new optimized, rapid, and accurate liquid chromatography method is also established for simultaneous determination of sildenafil citrate, tadalafil, and apomorphine hydrochloride in pharmaceutical preparations and bulk powders. The chromatographic separation of the three pharmaceuticals was achieved on a calixarene column in less than 10 min using a binary mobile phase of 35% acetonitrile and 65% 50 mM sodium perchlorate pH2.5 at 1 mL/min flow rate. The method was validated for system efficiency, linearity, accuracy, precision, limits of detection and quantitation, specificity, stability, and robustness. Statistical analysis proved that the method enabled reproducible and selective quantification of all three analytes in bulk drugs and in pharmaceutical preparations.

  2. Electrochemical behavior of folic acid at calixarene based chemically modified electrodes and its determination by adsorptive stripping voltammetry

    Energy Technology Data Exchange (ETDEWEB)

    Vaze, Vishwanath D. [Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai 400098 (India); Srivastava, Ashwini K. [Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai 400098 (India)], E-mail:


    Voltammetric behavior of folic acid at plain carbon paste electrode and electrode modified with calixarenes has been studied. Two peaks for irreversible oxidation were observed. Out of the three calixarenes chosen for modification of the electrodes, p-tert-butyl-calix[6]arene modified electrode (CME-6) was found to have better sensitivity for folic acid. Chronocoulometric and differential pulse voltammetric studies reveal that folic acid can assemble at CME-6 to form a monolayer whose electron transfer rate is 0.00273 s{sup -1} with 2-electron/2-proton transfer for the peak at +0.71 V against SCE. An adsorption equilibrium constant of 5 x 10{sup 3} l/mol for maximum surface coverage of 2.89 x 10{sup -10} mol/cm{sup 2} was obtained. The current is found to be rectilinear with concentration by differential pulse voltammetry. However, linearity in the lower range of concentration 8.79 x 10{sup -12} M to 1.93 x 10{sup -9} M with correlation coefficient of 0.9920 was achieved by adsorptive stripping voltammetry. The limit of detection obtained was found to be 1.24 x 10{sup -12} M. This method was used for the determination of folic acid in a variety of samples, viz. serum, asparagus, spinach, oranges and multivitamin preparations.

  3. Development of a pharmaceutical form containing calixarene molecules for the treatment of intact or injured skin contaminated by uranium; Developpement d'une forme pharmaceutique vehiculant un calixarene destinee au traitement d'une peau saine ou lesee contaminee par de l'uranium

    Energy Technology Data Exchange (ETDEWEB)

    Spagnul, A.


    The first objective of this research thesis was to develop a formulation containing a tricarboxylic calixarene for cutaneous application for the local treatment of skin contamination by uranium. A second objective is to assess the efficiency of a calixarene nano-emulsion for such a treatment. In a first part, the author proposes an overview of risks associated with skin contamination by uranium, and of current treatments and treatments under development. In the second part, the author presents the oil-in-water-type nano-emulsion, reports an in vitro assessment of the decontamination efficiency of the calixarene nano-emulsion, reports an in vivo assessment of this efficiency (on pig ear skin explants contaminated by uranium), and presents the main publications and a patent request related to this research work

  4. Calixarene receptors in the selective separation of alachlor. Characterization of the separated complexes; Receptores calixarenicos en la separacion selectiva de alaclor. Caracterizacion de los complejos separados

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, M.C


    Pesticides have been necessary in the agriculture since the plagues control have been remedied thanks to them but it has also provoked pollution. Nowadays, there are several methods which help to decrease or remedy such a pollution provoked. Unfortunately, any of them work out the environmental problem totally. Therefore, alternatives have to be found. The organic and tri dimensional characteristics of these macrocycles afford them a high versatility in such a way that these hosts can interact with organic guests selectively. Alachlor is a chlorinated organic herbicide useful in the plagues control of annual grasses and many broad-leave weeds which grow in maize, peanuts and soyabean. The ability of calixarenes to host organic guests with chemical characteristics similar to pesticides let them to be good candidates to compete with others methods which are used presently to separate organic pesticides. In this direction one of the advantages of proposing the use of calixarenes is, its facility of being modified in the lower and/or upper rims, to adapt them to aqueous, organic, gaseous and aqueous-organic media. Once the characteristics of reagents informed in the literature were confirmed and complemented with others found in this work, we studied, in solution, the interaction of the calixarenes with alachlor using 1 x 10{sup -5} to 1 x 10{sup -3} M solutions in acetonitrile for calixarenes fitted with phosphinoyl pendant arms in the lower rim, B{sub n}bL{sup n}, n= 4, 6) and in chloroform for parents calixarenes (H{sub n}bL{sup n} n = 4, 6, 8). Meticulous studies monitored by UV-Vis and luminescence were carried out, and the best stoichiometry to be used in further studies resulted to be 1(host): 1(alachlor). Therefore, we chose the 1 x 10{sup -4} M concentration to find how long the host-guest should be interacting in order to guarantee the formation in solution of the calixarene-alachlor species. It was found 168 h for the alachlor-B{sub n}bL{sup n} interaction

  5. A kinetic study of guest displacement reactions on a host-guest complex with a photoswitchable calixarene. (United States)

    Letzel, Matthias C; Schäfer, Christian; Novara, Francesca R; Speranza, Maurizio; Rozhenko, Alexander B; Schoeller, Wolfgang W; Mattay, Jochen


    The displacement processes of several guests, incorporated in a calixarene host system, were investigated in the gas phase by electrospray ionization-Fourier transform-ion cyclotron resonance (ESI-FT-ICR) mass spectrometry. The complexes resulting from a resorcin[4]arene host with ammonia and sec-butylamine guests were isolated in an ICR-cell, separately using both states of the photoswitch as well as two reference systems for the open and closed forms of the photoswitchable host. The isolated complexes were forced to exchange the guest by using methylamine, ethylamine and sec-butylamine, resulting in different reaction rates for all the measured systems. Especially, the reaction rates of both states of the photoswitch are dependent on the provided guest. Potential side effects like proton exchanges were examined by an H/D-exchange experiment. The results were investigated and supported by quantum chemical calculations (DFT).

  6. Calixarene receptors in the selective separation of alachlor. Characterization of the separated complexes; Receptores calixarenicos en la separacion selectiva de alaclor. Caracterizacion de los complejos separados

    Energy Technology Data Exchange (ETDEWEB)

    Garcia G, M.C


    Pesticides have been necessary in the agriculture since the plagues control have been remedied thanks to them but it has also provoked pollution. Nowadays, there are several methods which help to decrease or remedy such a pollution provoked. Unfortunately, any of them work out the environmental problem totally. Therefore, alternatives have to be found. The organic and tri dimensional characteristics of these macrocycles afford them a high versatility in such a way that these hosts can interact with organic guests selectively. Alachlor is a chlorinated organic herbicide useful in the plagues control of annual grasses and many broad-leave weeds which grow in maize, peanuts and soyabean. The ability of calixarenes to host organic guests with chemical characteristics similar to pesticides let them to be good candidates to compete with others methods which are used presently to separate organic pesticides. In this direction one of the advantages of proposing the use of calixarenes is, its facility of being modified in the lower and/or upper rims, to adapt them to aqueous, organic, gaseous and aqueous-organic media. Once the characteristics of reagents informed in the literature were confirmed and complemented with others found in this work, we studied, in solution, the interaction of the calixarenes with alachlor using 1 x 10{sup -5} to 1 x 10{sup -3} M solutions in acetonitrile for calixarenes fitted with phosphinoyl pendant arms in the lower rim, B{sub n}bL{sup n}, n= 4, 6) and in chloroform for parents calixarenes (H{sub n}bL{sup n} n = 4, 6, 8). Meticulous studies monitored by UV-Vis and luminescence were carried out, and the best stoichiometry to be used in further studies resulted to be 1(host): 1(alachlor). Therefore, we chose the 1 x 10{sup -4} M concentration to find how long the host-guest should be interacting in order to guarantee the formation in solution of the calixarene-alachlor species. It was found 168 h for the alachlor-B{sub n}bL{sup n} interaction

  7. Anti-tumor agent calixarene 0118 targets human galectin-1 as an allosteric inhibitor of carbohydrate binding (United States)

    Dings, Ruud P.M.; Miller, Michelle C.; Nesmelova, Irina; Astorgues-Xerri, Lucile; Kumar, Nigam; Serova, Maria; Chen, Xuimei; Raymond, Eric; Hoye, Thomas R.; Mayo, Kevin H.


    Calix[4]arene compound 0118 is an angiostatic agent that inhibits tumor growth in mice. Although 0118 is a topomimetic of galectin-1-targeting angiostatic amphipathic peptide anginex, we had yet to prove that 0118 targets galectin-1. Galectin-1 is involved in pathological disorders like tumor endothelial cell adhesion and migration and therefore presents a relevant target for therapeutic intervention against cancer. Here, 15N-1H HSQC NMR spectroscopy demonstrates that 0118 indeed targets galectin-1 at a site away from the lectin’s carbohydrate binding site, and thereby attenuates lactose binding to the lectin. Flow cytometry and agglutination assays show that 0118 attenuates binding of galectin-1 to cell surface glycans, and the inhibition of cell proliferation by 0118 is found to be correlated with the cellular expression of the lectin. In general, our data indicate that 0118 targets galectin-1 as an allosteric inhibitor of glycan/carbohydrate binding. This work contributes to the clinical development of anti-tumor calixarene compound 0118. PMID:22575017

  8. Simulation of cesium nitrate extraction by a calixarene. Application to supported liquid membranes transport; Modelisation de l`extraction du nitrate de cesium par un calixarene. Application a la modelisation du transport a travers des membranes liquides supportees

    Energy Technology Data Exchange (ETDEWEB)

    Sorel, C.


    This work fits into the general pattern of the CEA studies on the decontamination of liquid effluents containing long-lived radioactive isotopes. Some calixarenes have proved to be very effective to selectively extract the cesium of aqueous solutions whose composition simulates those of the effluents to be reprocessed. On account of the difficulty of the studied extraction mechanisms, a physical and chemical simulation has been necessary. The system takes into account: 1)a concentrated nitric acid aqueous phase and/or sodium nitrate 2)an organic phase constituted by the diluent 1,2-nitro-phenyl-octyl-ether and 1,3-diisopropoxy-calix(4)arene-couronne-6. The use of concentrated aqueous solutions requires to take into account variations to ideality by the mean of activity coefficients reckoning. The different theories on the reckoning of variations to ideality in aqueous or organic phases are described in the first part. The determination of cesium and sodium nitrates activity coefficients in very concentrated matrices has required an important theoretical and experimental study which is given in the second part. The aim of this study was indeed to complete the thermodynamic data of cesium and sodium nitrates aqueous solutions. The computerized tools required for the modeling are reviewed. The stoichiometry of the extracted species in the organic phase has been determined in the third part. The supported membrane technique is an original method of separation by liquid-liquid extraction. A membrane transport model has been developed and is given in the last part of this work. (O.M.). 128 refs.

  9. Alkaline-Side Extraction of Cesium from Savannah River Tank Waste Using a Calixarene-Crown Ether Extractant

    Energy Technology Data Exchange (ETDEWEB)

    Bonnesen, P.V.; Delmau, L.H.; Haverlock, T.J.; Moyer, B.A.


    Results are presented supporting the viability of the alkaline-side CSEX process as a potential replacement for the In-Tank Precipitation process for removal of cesium from aqueous high-level waste (HLW) at the Savannah River Site (SRS). Under funding from the USDOE Efficient Separations and Crosscutting program, a flowsheet was suggested in early June of 1998, and in the following four months, this flowsheet underwent extensive testing, both in batch tests at ORNL and ANL and in two centrifugal-contactor tests at ANL. To carry out these tests, the initial ESP funding was augmented by direct funds from Westinghouse Savannah River Corporation. The flowsheet employed a solvent containing a calixarene-crown hybrid compound called BoBCalixC6 that was invented at ORNL and can now be obtained commercially for government use from IBC Advanced Technologies. This special extractant is so powerful and selective that it can be used at only 0.01 M, compensating for its expense, but a modifier is required for use in an aliphatic diluent, primarily to increase the cesium distribution ratio D{sub Cs} in extraction. The modifier selected is a relatively economical fluorinated alcohol called Cs3, invented at ORNL and so far available. only from ORNL. For the flowsheet, the modifier is used at 0.2 M in the branched aliphatic kerosene Isopar{reg_sign} L. Testing at ORNL and ANL involved simulants of the SRS HLW. After extraction of the Cs from the waste simulant, the solvent is scrubbed with 0.05 M HNO{sub 3} and stripped with a solution comprised of 0.0005 M HNO{sub 3} and 0.0001 M CsNO{sub 3}. The selection of these conditions is justified in this report, both on the basis of experimental data and underlying theory.

  10. The effect of "on/off" molecular switching on the photophysical and photochemical properties of axially calixarene substituted activatable silicon(iv)phthalocyanine photosensitizers. (United States)

    Güngör, Ömer; Altınbaş Özpınar, Gül; Durmuş, Mahmut; Ahsen, Vefa


    Silicon(iv) phthalocyanines ( and ) bearing two calixarene groups as axial ligands were synthesized. Surprisingly, both phthalocyanines were obtained as two different isomers ( and ) depending on the distance between calixarene benzene groups and the phthalocyanine ring. DFT and TD-DFT computations were performed to model plausible structures of these isomers and to simulate electronic absorption spectra. These isomers converted into each other depending on the polarity of the used solvent, temperature and light irradiation. The photophysical and photochemical properties of each isomer were investigated in dimethylsulfoxide (DMSO) for the determination of photodynamic therapy (PDT) activities of these compounds. The more blue-shifted isomers ( and ) showed higher fluorescence quantum yields and singlet oxygen generation compared to more red-shifted counterparts ( and ). This behavior is extremely important for developing activatable photosensitizers for cancer treatment by PDT. Although these photosensitizers produce lower singlet oxygen in normal cells, they produce higher singlet oxygen (six times higher for ) in cancer cells since these photosensitizers converted to more blue-shifted isomers by using light irradiation.

  11. Removal of cesium from nuclear liquid waste using hybrid organic-inorganic membranes grafted by immobilized calixarenes; Synthese et caracterisation de membranes hybrides organo-minerales contenant des calixarenes. Application au traitement des effluents radioactifs

    Energy Technology Data Exchange (ETDEWEB)

    Duhart, A


    The aim of the Actinex program is to reduce massively the noxiousness of the vitrified wastes mainly due to actinides and other long-lived fission products such as {sup 129}I, {sup 99}Tc or {sup 135}Cs. Specific treatment means applicable to the industrial processes of spent fuel reprocessing have to be defined. The selective extraction of these radioelements for their transmutation or packaging in specific matrices is one of the research theme of this program. Different studies allowing the extraction of radioelements such as cesium, americium and plutonium by preferential diffusional transport through a supported liquid membrane of complexes (formed between a selective transport compound and the radioelements) are at the present time carried out in the ETPL (Effluents Treatment Processes Laboratory). Calix-4-arenes mono/bis-crown-6 are used as selective transport compounds. Meanwhile the possible losses of the selective transport compound by dissolution in the aqueous phases have oriented our researches towards a solid material in which the selective transport compound is chemically bound or trapped in the matrix. The transport compound is a calixarene, dissymmetrical and double grafted. It has been specifically synthesized for this study. It allows both to complex the cesium and to chemically bind a hetero-poly-siloxane. These monomers have poly-condensable groups which lead by sol-gel process to the formation of a three-dimensional bonds lattice. The matrix, thus obtained, can be supported either on a mineral material or on a porous organic material. Pre-polymers and the deposited layers have been characterized and correlations between the materials preparation and their properties, applied to cesium extraction, have been established. Experiments of cesium transfer through the solid membrane containing between 2 to 40% of selective transport compound, located between 2 compartments containing upstream, an acidic solution with strong salinity doped with Cs 137

  12. Separation of Calixarenes and Calixcrowns with a C60 Bonded Silica Stationary Phase in Normal _ Phase Liquid Chromatography%用C60键合硅胶固定相液相色谱分离杯芳烃及杯芳冠醚类化合物

    Institute of Scientific and Technical Information of China (English)

    冯钰; 胡玉玲; 李建森; 刘英; 达世禄; 陈远荫


    Separations of calixarenes and calixcrowns have been investigated on self made C60 bonded silica phase with isopropanol cyclohexane, chloroform-cyclohexane and dichloromethane-cyclohexane as mobile phase. The retention of the calixarenes and calixcrowns decreased with increasing the content of polar solvent in the mobile phase. Of the three polar solvents, isopropanol was found to be the strongest solvent for elution of the calixarenes and calixcrowns on the C60 bonded silica. The separation selectivity of the C60 bonded silica stationary phase for the calixarenes and calixcrowns was depended on the polar solvents. A good separation of the calixarenes and calixcrowns on the C60 bonded silica stationary phase was achieved by using an appropriate mobile phase.%以自合成的C60键合硅胶液相色谱固定相,分别选用3种不同选择性的流动相体系:异丙醇-环己烷,氯仿-环己烷和二氯甲烷-环己烷,考察了流动相组成对杯芳烃及杯芳冠醚化合物保留行为和分离选择性的影响。在一定的流动相条件下溶质能得到较好分离。

  13. On-cartridge derivatisation using a calixarene solid-phase extraction sorbent for facile, sensitive and fast determination of formaldehyde in beer. (United States)

    Deng, Zhifen; Hu, Kai; Zhang, Yongming; Zhao, Wenjie; Wang, Fei; Guo, Ling; Zhang, Wenfen; He, Juan; Huang, Yanjie; Zhang, Shusheng


    This work demonstrates the successful application of an on-cartridge derivatisation procedure for facile, fast and sensitive determination of formaldehyde in beer by HPLC-UV. The derivatisation and solid-phase extraction (SPE) were integrated into a novel calixarene SPE sorbent: tetraazacalix[2]arene[2]triazine bonded silica gel. Specifically, 2,4-dinitrophenylhydrazine was adsorbed onto the sorbent in advance, based on the charge-transfer interaction between the macrocyclic molecule and nitrobenzenes. The method was optimised and validated: under the optimal conditions of derivatisation, SPE and HPLC separation, good linearity was obtained in the range of 0.080-3.2μgmL(-1) with a correlation coefficient of 0.9939, the limit of detection was 3.0ngmL(-1) (S/N=3), the limit of quantification was 10ngmL(-1) (S/N=10), and the recovery level using this method was desirable at 75-84%. The developed method was successfully applied to determine formaldehyde content in real beer samples; the results were in the range of 0.11-1.1μgmL(-1).

  14. The Nature of Aqueous Solutions of a Cationic Calix[4]arene: A Comparative Study of Dye–Calixarene and Dye–Surfactant Interactions

    Directory of Open Access Journals (Sweden)

    V. I. Kalchenko


    Full Text Available Among different types of calixarenes, the water–soluble ones are of especial interestbecause of their possible applications in biochemical research. In order to elucidate the natureof aqueous solutions of a cationic amphiphilic calixarene, substituted tetrapropoxycalix[4]arene bearing hydrophilic choline groups at the upper rim, we studied vis–spectroscopically the influence of the above system on the acid–base behavior of threeindicator dyes, namely, 2,4-dinitrophenol, bromophenol blue, and N,N/-dioctadecylrhodamine,at constant ionic strength of 0.05 M, maintained with NaCl addition. Simultaneously,‘apparent’ ionization constants, Kaa , of the same dyes were determined in the presence ofcommon cationic surfactant micelles. Within the concentration range from 1.0×10–5 to 0.01 M,the aforementioned water–soluble calixarene displays effects similar to those of micelles ofcetyltrimethylammonium bromide (or chloride. The shifts of the absorption and emissionbands in the visible region, as well as the alterations of the Kaa values against the ‘aqueous’ones appeared to be very similar in aqueous solutions of both calix[4]arene and cationicsurfactant. A conclusion can be made about aggregation (or association, i.e., micelleformation of the cationic calix[4]arene under study.

  15. Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides; Modelisation thermodynamique de l'extraction de nitrates de lanthanides par le CMPO et par un calixarene-CMPO en milieu acide nitrique concentre. Application a l'optimisation de la separation des lanthanides et des actinides/lanthanides

    Energy Technology Data Exchange (ETDEWEB)

    Belair, S


    The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO{sub 3}){sub 3}-HNO{sub 3}-H{sub 2}O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

  16. Modeling a calixarene-crown-6 and its alkali complexes by means of a hybrid quantum mechanical/molecular mechanical method; Modelisation d'un calixarene-couronne-6 et de ses complexes alcalins par une methode hybride mecanique quantique/ mecanique moleculaire

    Energy Technology Data Exchange (ETDEWEB)

    Lamare, V.; Golebiowski, J. [CEA Cadarache, Dept. d' Entreposage et de Stockage des Dechets (DCC/DESD/SEP), 13 - Saint-Paul-lez-Durance (France); Ruiz-Lopez, M.F.; Martins-Costa, M.; Millot, C. [Universite Henri Poincare - Nancy I (UMR CNRS-UHP 7565), 54 - Nancy (France)


    Calixarene-crown-6s in 1,3-alternate conformation are compounds currently investigated for their ability to selectively extract traces of cesium from acidic or strong salinity aqueous solutions. Studies based on molecular modeling were undertaken on these systems to understand their behavior regarding cesium and other alkali cations, in particular sodium. In this work, a recently developed molecular modeling approach was used to investigate calixarene BC6 and its alkali complexes. The whole calixarene ligand is treated by the semiempirical AM1 quantum method (QM) whereas the cation and solvent are treated by a conventional force field (MM). The total energy of the system is the sum of the QM and MM sub-system contributions plus the QM/MM interaction energy. The latter includes the electrostatic interaction between QM charges (nuclei + electrons) and MM sites, and the non-electrostatic QM/MM van der Weals term, usually expressed by a Lennard-Jones potential. In the QM/MM method, van der Waals interactions between the QM and MM sub-systems are described by empirical Lennard-Jones parameters which must be adapted to the hybrid potential considered. Parameters on oxygen atoms were optimized. For the cations, two sets of Parameters were tested: Aqvist empirical parameters, derived to represent cation/water interactions in classical dynamics (set 2), and a new set of parameters which we calculated from dispersion coefficients available in the literature (set 1). The latter gave better results for the interactions with the crown. In the sodium complex, the cation interacts with only four oxygen atoms of the crown, whereas in the complex with cesium, the interaction involves six oxygen atoms. Distortion of the BC6 is therefore less with sodium and favors the corresponding complex by 4 kcal/mol. The cation/BC6 van der Waals energy is very weak for the two complexes. Hence the interaction between the cation and BC6 is primarily electrostatic. The BC6 polarization energy due

  17. Structural study of the uranyl and rare earth complexation functionalized by the CMPO; Etude structurale de la complexation de l'uranyle et des ions lanthanides par des calixarenes fonctionnalises par le CMPO

    Energy Technology Data Exchange (ETDEWEB)

    Cherfa, S


    In view of reducing the volume of nuclear waste solutions, a possible way is to extract simultaneously actinide and lanthanide ions prior to their ulterior separation.. Historically, the two extractant families used for nuclear waste reprocessing are the phosphine oxides and the CMPO (Carbamoyl Methyl Phosphine Oxide). For a better understanding of the complexes formed during extraction, we undertook structural studies of the complexes formed between uranyl and lanthanide (III) ions and the two classes of ligands cited above. These studies have been performed by X-ray diffraction on single crystals. Recently, a new type of extractants of lanthanide (III) and actinide (III) ions has been developed. When the Organic macrocycle called calixarene (an oligomeric compound resulting from the poly-condensation of phenolic units) is functionalized by a CMPO ligand, the extracting power, in terms of yield and selectivity towards lightest lanthanides, is greatly enhanced compared to the one measured for the single CMPO. Our X-ray diffraction studies allowed us to characterise, in terms of stoichiometry and monodentate or bidentate coordination mode of the CMPO functions, the complexes of calix[4]arene-CMPO (with four phenolic units) with lanthanide nitrates and uranyl. These different steps of characterisation enabled us to determine the correlation between the structures of the complexes and both selectivity and exacerbation of the extracting power measured in the liquid phase. (author)

  18. Multiscale Analysis of the Migration and Influence of the Residual Solvent in Methyl Methacrylate-Acrylamide Calixarene Polymer Film%残留溶剂在PMMA-CA聚合物膜中迁移及影响的多尺度分析

    Institute of Scientific and Technical Information of China (English)

    刘满华; 陈维霞; 黄民


    Studies on the effect of dopants on the functional polymers are of great academic and practical importance.This study is to explore the influence of glassy and rubbery states of polymer on the solvent diffusion and the effect of residual solvent on the protonization energy of calixarene (CA) by using molecular dynamics and quantum mechanics calculations, respectively. Molecular dynamics (MD) simulation of the glass transition temperature of methyl methacrylate-acrylamide calixarene was performed based on the theory of free volume. The obtained free volume-temperature curve indicates that the glass transition temperature is about 395 K, which is in good agreement with that from the literature.The mean square displacement (MSD) curves were obtained at different temperatures in both glassy and rubbery state by using MD method. The MSD results indicate that the diffusion coefficients are much smaller in glassy state than in rubbery state. The effect of residual solvent on the protonization energy of CA was calculated by using density functional theory (DFT) method. The results indicate that the presence of solvent could enhance the degree of the protonization of the calixarene in polymer,but it is much weaker than MMA copolymer.%  杂质对功能高分子聚合物理化性质的影响具有重要的学术价值与应用意义.今分别通过分子动力学(Molecular Dynamics, MD)及密度泛函(Density Functional Theory, DFT)等方法探索了聚合物玻璃态和橡胶态下溶剂扩散系数的不同以及残留溶剂对聚合物分子解离能的影响.根据自由体积理论,对聚甲基丙烯酸甲酯-丙烯酰胺杯芳烃(PMMA-CA)的玻璃化温度进行了分子动力学(MD)模拟,得到的自由体积与温度的关系曲线显示其玻璃化温度为395K.考察了玻璃态和橡胶态下溶剂扩散系数的不同,MD模拟得到的均方位移(Mean Square Displacement, MSD)曲线显示,聚合物在玻璃态下溶剂的自扩散系数远低于橡胶态

  19. Review on calixarene-type macrocycles and metal extraction data

    Energy Technology Data Exchange (ETDEWEB)

    Ludwig, R. [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment


    This paper gives an overview on the current state of solvent extraction studies with derivatized [1.n]-metacyclophanes and related compounds. 122 References from the last ten years are discussed and data on extractability, extraction equilibria, and complex formation are presented in graphical form. (author) 122 refs.

  20. Comparative Study of Protein Immobilization Properties on Calixarene Monolayers

    Directory of Open Access Journals (Sweden)

    Kwangnak Koh


    Full Text Available Three calix[4]arene (Cal-4 derivatives of which contain ethylester (1,carboxylic acid (2, and crownether (3 at the lower rim with a common reactive thiol at theupper rim were synthesized and constructed to self-assembled monolayers (SAMs on Aufilms. After spectroscopic characterization of monolayers, the interaction between Cal-4and surface confined bovine serum albumin (BSA in the SAMs was analyzed by surfaceplasmon resonance (SPR. The estimated surface concentration of BSA on the Cal-4 SAMwith crownether group was the highest among the three Cal-4 derivatives. Anti-hIgG andhIgG pair was employed for the investigation of protein-protein interaction. Molecularinteraction between anti-hIgG and hIgG can be detected in a concentration range of 10pg/mL to 200 pg/mL on the Cal-4 derivative 3 SAM modified SPR chip.

  1. Excitation Dynamics in Hetero-bichromophoric Calixarene Systems. (United States)

    Tosi, Irene; Segado Centellas, Mireia; Campioli, Elisa; Iagatti, Alessandro; Lapini, Andrea; Sissa, Cristina; Baldini, Laura; Cappelli, Chiara; Di Donato, Mariangela; Sansone, Francesco; Santoro, Fabrizio; Terenziani, Francesca


    In this work, the dynamics of electronic energy transfer (EET) in bichromophoric donor-acceptor systems, obtained by functionalizing a calix[4]arene scaffold with two dyes, was experimentally and theoretically characterized. The investigated compounds are highly versatile, due to the possibility of linking the dye molecules to the cone or partial cone structure of the calix[4]arene, which directs the two active units to the same or opposite side of the scaffold, respectively. The dynamics and efficiency of the EET process between the donor and acceptor units was investigated and discussed through a combined experimental and theoretical approach, involving ultrafast pump-probe spectroscopy and density functional theory based characterization of the energetic and spectroscopic properties of the system. Our results suggest that the external medium strongly determines the particular conformation adopted by the bichromophores, with a direct effect on the extent of excitonic coupling between the dyes and hence on the dynamics of the EET process itself.

  2. Calixtyrosol: a Novel Calixarene Based Potent Radical Scavenger


    Nasuhi Pur, Fazel; Akbari Dilmaghani, Karim


    The oxidative stress causes many diseases in human, therefore antioxidants have a special position in the medicinal chemistry. Tyrosol is an important antioxidant with a plenty of biological properties. There are many strategies such as clustering single drug units in order to develop new drugs. The cluster effect can increase drug effects relative to single drug unit. Calixtyrosol is the novel cluster of tyrosol that shows a more effective antioxidant activity than single tyrosol. In fact, t...

  3. Calixtyrosol: a Novel Calixarene Based Potent Radical Scavenger. (United States)

    Nasuhi Pur, Fazel; Akbari Dilmaghani, Karim


    The oxidative stress causes many diseases in human, therefore antioxidants have a special position in the medicinal chemistry. Tyrosol is an important antioxidant with a plenty of biological properties. There are many strategies such as clustering single drug units in order to develop new drugs. The cluster effect can increase drug effects relative to single drug unit. Calixtyrosol is the novel cluster of tyrosol that shows a more effective antioxidant activity than single tyrosol. In fact, tyrosol can be considered as 1/4 of the cluster. Four hydroxyethyl moieties have been grafted at the upper rim of the calix[4]arene in all-syn orientation, giving novel agent in the field of antioxidant agents. Free radical scavenging tests were determined by the 2, 2-diphenyl-1-picrylhydrazyl radical in methanol for four antioxidants: calixtyrosol, tyrosol, hydroxytyrosol and 3, 5-di-tert-buty l-4-hydroxytoluene to compare their antioxidant activity. Free radical scavenging test showed that calixtyrosol has enhanced antioxidant activity in comparison to the corresponding single tyrosol unit (> 5 fold), it has even more active than the other test antioxidants (2 fold). Presumably, it is attributed to tethering and arraying of four impacted tyrosol units, which make a synergistic effect in interactions with radicals for creating effective radical scavenging activity. This method is in debt of synergistic effect, tethering and arraying of single units in the cluster structure.

  4. Selective extraction of actinides by calixarenes: application to bioassay analysis; Extraction selective des actinides par les calixarenes: application a l'analyse radiotoxicologique

    Energy Technology Data Exchange (ETDEWEB)

    Boulet, B


    In the context of nuclear workers monitoring, the aim of this PhD was to selectively isolate U, Pu, and Am from urine to propose a new analytical procedure to the Medical and Biology Analysis Laboratories. The 1,3,5-OCH{sub 3}-2,4,6-OCH{sub 2}CONHOH-p-tert-butyl-calix[6]arene molecule has been selected as a promising extractant for U, Pu, and Am. Its physico-chemical properties and its affinity for UO{sub 2}{sup 2+} have been studied through two approaches, one theoretical (molecular modelling at DFT level), and one experimental. The extractions of the three actinides by the hydroxamic calix[6]arene were quantitative in liquid-liquid and solid-liquid systems. Their separation has also been shown possible and efficient. After optimization, the proposed procedure should allow the laboratories to carry out the chemical treatment of urine, before the measurement, in one day instead of the three days needed nowadays. (author)

  5. Calixarene-stabilised cobalt nanoparticle rings: Self-assembly and collective magnetic properties

    DEFF Research Database (Denmark)

    Wei, A; Tripp, SL; Liu, J


    ) and entropic loss, analogous to the thermodynamic balance of forces governing supramolecular self-assembly. Examination of the Co nanoparticle rings by electron holography (an electron microscopy technique for imaging in-plane magnetic induction) reveals the existence of chiral flux closure (FC) domains...... at room temperature, comprising a 'racemic' mixture of clockwise and anticlockwise states. Furthermore, these FC polarisations can be reversed by applying out-of-plane magnetic pulses (Hz) in alternating directions. This switching behaviour has no known analogy at the macroscopic level, and may represent...

  6. Interfacial binding of divalent cations to calixarene-based Langmuir monolayers. (United States)

    Tulli, Ludovico G; Wang, Wenjie; Lindemann, William R; Kuzmenko, Ivan; Meier, Wolfgang; Vaknin, David; Shahgaldian, Patrick


    The interactions of Langmuir monolayers produced through the self-assembly of an amphiphilic p-carboxycalix[4]arene (1) with a series of divalent, fourth-period transition metals, at the air-water interface, were investigated. Changes in the interfacial behavior of 1 in response to the presence of CuCl2, CoCl2, MnCl2, and NiCl2 were studied by means of Langmuir compression isotherms and Brewster angle microscopy (BAM). The measurements revealed that the self-assembly properties of 1 are significantly affected by Cu(2+) ions. The interactions of 1-based monolayers with Co(2+) and Cu(2+) ions were further investigated by means of synchrotron radiation-based X-ray reflectivity (XRR), X-ray near-total-reflection fluorescence (XNTRF), and grazing incidence X-ray diffraction (GIXD). XNTRF and XRR analyses revealed that the monolayer of 1 binds more strongly to Cu(2+) than Co(2+) ions. In the presence of relatively high concentrations of Cu(2+) ions in the subphase (1.4 × 10(-3) M), XNTRF exhibited anomalous depth profile behavior and GIXD measurements showed considerably strong diffuse scattering. Both measurements suggest the formation of Cu(2+) clusters contiguous to the monolayer of 1.

  7. Calixarene based chiral solvating agents for α-hydroxy carboxylic acids (United States)

    Bozkurt, Selahattin


    Novel chiral calix[4]arene derivatives functionalized at the lower rim have been prepared from the reaction of p-tert-butylcalix[4]arene diamine derivative with N-Phthaloyl-L-phenylalanine or (2S)-2-((benzyloxy)carbonyl)amino)-3-hydroxypropanoic acid or (2S,3R)-2-((benzyloxy)carbonyl)amino-3-hydroxybutanoic acid in 63-81% yield. The structures of these receptors were characterized by FTIR, 1H, 13C and 2D COSY NMR spectroscopy. The enantioselective recognition of these receptors towards the enantiomers of racemic carboxylic acids was studied by 1H NMR spectroscopy. The molar ratios of the chiral compounds with each of the enantiomers of guests were determined by using Job plots. The Job plots indicate that the hosts form 1:2 instantaneous complexes with all guests. The receptors exhibited different chiral recognition abilities toward the enantiomers of racemic guests. NMR studies demonstrated that the receptors function as highly effective chiral shift reagents for determining the enantiomeric purity of a series of carboxylic acids.

  8. Study of the Molecular Recognition of Nucleotides and Bases by a Novel Calixarene Derivative Containing Uracil

    Institute of Scientific and Technical Information of China (English)

    SHI,Hui-Jie; SHI,Xian-Fa; YAO,Tian-Ming; JI,Liang-Nian


    A calix[4]arene derivative containing uracil, 5-(uracil-N1-acetamido)-25,26,27,28-tetrahy droxycalix[4]-arene (UC), was designed and synthesized. The interaction with nucleotides and bases has also been studied by ESI-MS and π-A isotherms. The results of ESI-MS showed that UC could recognize adenine and adenosine from other nucleotides and bases. In addition, π-A isotherms at the air-water interface indicated that there was interaction between UC and the species in the subphase, and the respective complexes were formed in the monolayer. The mean molecular area at zero surface pressure increased with the sizes of the nucleotides and bases in the subphase in the order: water<adenine<adenosine<ATP·Na2.

  9. Synthesis and Characterization of Calixarene Tetraethers: An Exercise in Supramolecular Chemistry for the Undergraduate Organic Laboratory (United States)

    Debbert, Stefan L.; Hoh, Bradley D.; Dulak, David J.


    In this experiment for an introductory undergraduate organic chemistry lab, students tetraalkylate tertbutylcalix[4]arene, a bowl-shaped macrocyclic oligophenol, and examine the supramolecular chemistry of the tetraether product by proton nuclear magnetic resonance (NMR) spectroscopy. Complexation with a sodium ion reduces the conformational…

  10. Protein-calixarene interactions: complexation of Bovine Serum Albumin by sulfonatocalix[n]arenes. (United States)

    Memmi, L; Lazar, A; Brioude, A; Ball, V; Coleman, A W


    The complexation of Bovine Serum Albumin with sulfonatocalix[n]arenes has been demonstrated by means of electrospray mass spectrometry, dynamic light scattering and atomic force microscopy; with sulfonatocalix[4]arene one strong and two weaker binding sites are detected; the effects on the structure of thin films formed by surface deposition of BSA show that the sulfonatocalix[n]arenes act to reticulate the films and produce essentially planar systems.

  11. Calix-arene silver nanoparticles interactions with surfactants are charge, size and critical micellar concentration dependent. (United States)

    Tauran, Yannick; Brioude, Arnaud; Shahgaldian, Patrick; Cumbo, Alessandro; Kim, Beomjoon; Perret, Florent; Coleman, Anthony W; Montasser, Imed


    The interactions of silver nanoparticles capped by various calix[n]arenes bearing sulphonate groups at the para and/or phenolic faces with cationic, neutral and anionic surfactants have been studied. Changes in the plasmonic absorption show that only the calix[4]arene derivatives sulphonated at the para-position interact and then only with cationic surfactants. The interactions follow the CMC values of the surfactants either as simple molecules or mixed micelles.

  12. Considerable fluorescence enhancement upon supramolecular complex formation between berberine and p-sulfonated calixarenes (United States)

    Megyesi, Mónika; Biczók, László


    Remarkably strong binding of berberine to 4-sulfonatocalix[8]arene was found in aqueous solution, which led to fluorescence quantum yield increase of a factor about 40 at pH 2. The hypsochromic shift of the fluorescence maximum implied that berberine sensed less polar microenvironment when confined to SCX8. The stability of the supramolecular complex significantly diminished when sulfocalixarenes of smaller ring size served as host compounds but the pH affected the association strength to a much lesser extent. All berberine complexes proved to be barely fluorescent at pH 12.2 because of excited state quenching by the hosts via electron transfer.

  13. New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, Richard A.


    The project objective was the discovery of new ligands for performing metal ion separations. The research effort entailed the preparation of new metal ion complexing agents and polymers and their evaluation in metal ion separation processes of solvent extraction, synthetic liquid membrane transport, and sorption. Structural variations in acyclic, cyclic, and bicyclic organic ligands were used to probe their influence upon the efficiency and selectivity with which metal ion separations can be performed. A unifying feature of the ligand structures is the presence of one (or more) side arm with a pendent acidic function. When a metal ion is complexed within the central cavity of the ligand, ionization of the side arm(s) produces the requisite anion(s) for formation of an overall electroneutral complex. This markedly enhances extraction/transport efficiency for separations in which movement of aqueous phase anions of chloride, nitrate, or sulfate into an organic medium would be required. Through systematic structural variations, new ligands have been developed for efficient and selective separations of monovalent metal ions (e.g., alkali metal, silver, and thallium cations) and of divalent metal ion species (e.g., alkaline earth metal, lead, and mercury cations). Research results obtained in these fundamental investigations provide important insight for the design and development of ligands suitable for practical metal ion separation applications.

  14. Molecular Design of Calixarene 5. Syntheses and Cation Selectivities of Novel Schiff' s Base p-tert-Butylcalix[4]arenes

    Institute of Scientific and Technical Information of China (English)

    刘育; 赵邦屯; 王浩; 陈企发; 张衡益


    Five novel Schiff's bases p-tert-butylcalix[4]arenes have ben synthesized in high yields by the reaction of 1,3-distally disubstituted p-tert-butyicalix[4]arene amine(1) with the corresponding aromatic aldehydes,and their cation binding abilities and selectivities with alkali and heavy metal ions have been evaluated by solvent extraction of aqueous metal picrates to show the highet Ag+ extractability for Schiff' s base p-tertbutylcalix[4]arene (6) and the best Na+/Li+ and Ag+/Tl+selectivities for Schiff's base p-tert-butylcalix[4]arene (4 and 2) over any other caltx[4]arene derivatives, respectively.

  15. Study of the Complexation Behavior of Calixarene with Transition Metal Cations by UV-vis and Fluorescent Spectra

    Institute of Scientific and Technical Information of China (English)

    YANG,Jun-Lin(杨俊林); ZHENG,Qi-Yu(郑企雨); AN,Li-Na(安丽娜); CHEN,Chuan-Feng(陈传峰); LIN,Hong-Zhen(蔺洪振); BAI,Feng-Lian(白凤莲); HUANG,Zhi-Tang(黄志镗)


    A new fluorescent compound based on calix[4]arene skeleton was synthesized. Its complexation ability with transition metal ions, such as Fe3+, Co2+, Ni2+, Cu2+, Zn2+ and Ag+, was investigated by UV-vis and fluorescent spectra.

  16. Study of the Complexation Behavior of Calixarene with Transition Metal Cations by UV—vis and Fluorescent Spectra

    Institute of Scientific and Technical Information of China (English)

    杨俊林; 郑企雨; 等


    A new fluorescent compound based on calix[4] arene skeleton was synthesized.Its complexation ability with transition metal ions,such as Fe3+,Co2+,Ni2+,Cu2+,Zn2+ and Ag+,Was investigated by UV-vis and fluorescent spectra.

  17. High-efficiency pyrene-based blue light emitting diodes: Aggregation suppression using a calixarene 3D-scaffold

    KAUST Repository

    Chan, Khaileok


    An efficient blue light emitting diode based on solution processable pyrene-1,3-alt-calix[4]arene is demonstrated, providing a record current efficiency of 10.5 cd A -1 in a simple non-doped OLED configuration. Complete suppression of pyrene aggregation in the solid state is achieved by controlling chromophore dispersion using the 1,3-alt-calix[4]arene scaffold. © 2012 The Royal Society of Chemistry.

  18. Comparing an ionic liquid to a molecular solvent in the cesium cation extraction by a calixarene: a molecular dynamics study of the aqueous interfaces. (United States)

    Sieffert, Nicolas; Wipff, Georges


    We report a molecular dynamics (MD) study of the interfacial behavior of key partners involved in the Cs(+) cation extraction by a calix[4]arene-crown-6 host (L), comparing an ionic liquid (IL) to a classical molecular solvent (chloroform) as receiving "oil" phase. The IL is composed of hydrophobic 1-butyl-3-methylimidazolium cations (BMI(+)) and bis(trifluoromethylsulfonyl)imide anions (Tf(2)N(-)) and forms a biphasic system with water. The simulations reveal similarities but also interesting differences between the two types of interfaces. Much longer times are needed to "equilibrate" IL systems, compared to classical liquid mixtures, and there is more intersolvent mixing with the IL than with chloroform, especially concerning the water-in-oil content. There is also some excess of the BMI(+) cations over the Tf(2)N(-) anions in the aqueous phase. Simulations on the Na(+)NO(3)(-) and Cs(+)NO(3)(-) ions show that they sometimes interact at the interface with the IL ions, forming hydrated intimate ion pairs, whereas they are "repelled" by the classical interface. The LCs(+) complex and L ligand also behave differently, depending on the "oil phase". They are better solvated by the IL than by chloroform and thus poorly attracted at the IL interface, whereas they adsorb at the chloroform interface, adopting well-defined amphiphilic orientations. The results are discussed in the context of assisted ion transfer and provide a number of arguments explaining the specificity and efficiency of IL based, compared to classical extraction systems.

  19. Determination of trace acrylamide in starchy foodstuffs by HPLC using a novel mixed-mode functionalized calixarene sorbent for solid-phase extraction cleanup. (United States)

    Zhang, Wenfen; Deng, Zhifen; Zhao, Wenjie; Guo, Ling; Tang, Wei; Du, Huifang; Lin, Lin; Jiang, Qiong; Yu, Ajuan; He, Lijun; Zhang, Shusheng


    In this paper, a rapid and effective HPLC method, using tetraazacalix[2]arene[2]triazine-modified silica gel (NCSi) as solid-phase extraction (SPE) sorbent, was developed for the purification and determination of trace acrylamide in starchy foodstuffs. The main influence factors of SPE including amount of NCSi sorbent, sample flow rate, and volume and composition of washing solution were investigated and evaluated in the sample pretreatment step. The optimized purification effect was achieved at the sample flow rate of 3 mL/min with 100 mg of NCSi and 2 mL of washing solution (water, 100%). The HPLC separation was carried out on a C18 column (250×4.6 mm i.d., 5 μm) with a mobile phase of methanol/water (10:90, v/v). The linear range of the calibration curve was 4-4000 ng/mL with s correlation coefficient of >0.9999. The intraday and interday RSDs (n=5) of peak areas of acrylamide were 0.22 and 0.90% and the intraday and interday RSDs (n=5) of retention times were 0.50 and 1.63%, respectively. In addition, overall recoveries through the extraction and NCSi-SPE purification ranged from 73.13 to 98%. Compared with the commercial SPE sorbents, NCSi featured excellent selectivity to retain polar and nonpolar interferences in the sample matrices. The improved method was simple, rapid, accurate, and promising for the determination of trace acrylamide in starchy foods with a complex matrix.

  20. Progress on the synthesis of heteroatom-bridged calixarenes%含多种杂原子的桥联杯芳烃的合成研究进展

    Institute of Scientific and Technical Information of China (English)

    张德春; 王文革



  1. 含单种杂原子的桥联杯芳烃的合成研究进展%Progress on the synthesis of single heteroatom-bridged calixarenes

    Institute of Scientific and Technical Information of China (English)

    张德春; 王文革



  2. Cavity-containing supramolecular gels as a crystallization tool for hydrophobic pharmaceuticals. (United States)

    Kaufmann, Lena; Kennedy, Stuart R; Jones, Christopher D; Steed, Jonathan W


    We present two approaches to low-molecular-weight supramolecular gels bearing hydrophobic cavities based on calixarene-containing building blocks. Gels are formed by a calixarene based tetrahydrazide gelator or a co-gel of a calixarene diammonium salt and a bis-crown ether. The calixarene hydrophobic cavity enables the complexation of hydrophobic drug molecules in a generic fashion thus providing an anchor site on the surface of the gel fibre to initiate drug crystal nucleation and growth. This technique potentially represents a route to growth of hard-to-nucleate polymorphic modifications. The co-gel comprising two components holding together by non-covalent ammonium-crown ether interaction can be easily switched back to the sol state by adding competitive binding cations.

  3. 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetramethoxycalix[4]arene dichloromethane hemisolvate

    Directory of Open Access Journals (Sweden)

    Edwin Weber


    Full Text Available In the title compound, C48H64O4·0.5CH2Cl2, both crystallographically independent calixarene molecules display a partial cone conformation. Their crystal packing is stabilized by C—H...π contacts involving the methoxy groups. The solvent molecule is located interstitially between two calixarene units with C—H...Cl contacts to methoxy and tert-butyl groups. One tert-butyl residue of each calixarene molecule is disordered over two positions (occupancies 0.60/0.40 and 0.63/0.37, resulting in bond distances that deviate from ideal values. The tetramer calixarene molecules present models with approximate non-crystallographic Cs symmetry.

  4. Preparation of new Calix[4]arene-immobilized biopolymers for enhancing catalytic properties of Candida rugosa lipase by sol-gel encapsulation. (United States)

    Ozyilmaz, Elif; Sayin, Serkan


    The article describes preparation of new calixarene biopolymers consisting of the immobilization of convenience calixarene derivative onto cellulose and chitosan biopolymers, and the encapsulation of these calixarene biopolymers with Candida rugosa lipase within a chemical inert sol-gel supported by polycondensation with tetraethoxysilane and octyltriethoxysilane. The catalytic properties of immobilized lipase were evaluated into model reactions employing the hydrolysis of p-nitrophenylpalmitate and the enantioselective hydrolysis of naproxen methyl esters from racemic prodrugs in aqueous buffer solution/isooctane reaction system. The resolution studies using sol-gel support have observed more improvement in the enantioselectivity of naproxen E = 300 with Cel-Calix-E than with encapsulated lipase without calixarene-based materials. Furthermore, the encapsulated lipase (Cel-Calix-E) was still retained about 39 % of their conversion ratios after the fifth reuse in the enantioselective reaction.

  5. Synthesis and Absorption Properties of Calix[6]amides-based Polymers

    Institute of Scientific and Technical Information of China (English)


    Reacting calix[6]arene hexaesters with poly(ethyleneimine), a series of calix [6]amides- based polymers were obtained for the first time.It is found that they show high absorption capacities towards soft cations comparing to hard cations, and the absorption abilities enhanced with the increasing of calixarene content, which may indicates the cavity of calixarene plays crucial role in absorption.Polymer 2c shows good selective absorption capability towards Ag+ among the tested cations.

  6. Synthesis and Characterization of Thiacalix [4] arene Derivatives with Polymerisable Groups

    Institute of Scientific and Technical Information of China (English)


    @@ Introduction Calixarenes are versatile host molecules for molecular recognition and supramolecular assembly because its functional groups can be readily introduced into the phenolic OH or the para position to realize a wide variety of functions[1-5]. During the past decade,calixarenes-based polymers received increasing attention as these polymers can be used to synthesize the materials that are suitable for the preparation of chemical sensor devices such as ion-selective electrodes or transport membranes[6-16].

  7. Determination of the extractive capacity of para-tert butyl calix[8]arene octa-phosphinoylated towards uranyl ions from an aqueous-acidic-salty medium; Determinacion de la capacidad extractiva del p-ter-butilocalix[8]areno octa-fosfinoilado hacia iones uranilo de un medio acuo-acido salino

    Energy Technology Data Exchange (ETDEWEB)

    Serrano V, E. C.


    The extraction properties of octa-phosphinoylated para-tert butyl calix[8]arene (prepared in the laboratory) in chloroform towards uranyl ions from an aqueous-acidic-salty medium (HNO{sub 3}-3.5 NaNO{sub 3}) containing uranyl nitrate salt, was investigated. Two spectroscopic techniques UV/Vis and Luminescence were used for this study. The latter permitted analyze the fluorescence from the uranyl ions influenced by the surrounding medium. Both permitted to learn about the power of this calixarene as extractant towards the mentioned ions. Its extraction ability or capability using this calixarene at 5.91 x 10{sup -4} M towards the uranyl ions was 400% as determined by UV/Vis while fluorescence revealed 100% of uranyl ion extraction. A closed analysis of the results obtained by using these techniques revealed that the stoichiometry of the main extracted species was 1calixarene:2 uranyl ions. The loading capacity of the calixarene ligand towards the uranyl ions was also investigated using both techniques. UV/Vis resulted to be inadequate for quantifying exactly the loading capacity of the calixarene whereas luminescence was excellent indeed, using a 5.91 x 10{sup -4} M calixarene concentration, its loading capacity was 0.157 M of free uranyl ions from 0.161 M of uranyl ions present in the aqueous-acidic-salty medium. The extracts from the ability and capacity studies were concentrated to dryness, purified and the dried extracts were analyzed by infrared and neutron activation analysis. By these techniques it was demonstrated that during the extraction of the uranyl ions by the calixarene ligand they form thermodynamically and kinetically stable complexes, since in the solid state, the 1:2, calixarene; uranyl ions stoichiometry was kept with the minimum formula: (UO{sub 2}){sub 2}B{sub 8}bL{sup 8}(NO{sub 3}){sub 4}(H{sub 2}O){sub 4}CHCl{sub 3}(CH{sub 3}OH){sub 3} the methanol molecules come from its purification. It is proposed that B{sub 8}bL{sup 8} calixarene in

  8. A multi-property fluorescent probe for the investigation of polymer dynamics near the glass transition

    NARCIS (Netherlands)

    Siekierzycka, J.R.; Hippius, C.; Würthner, F.; Williams, R.M.; Brouwer, A.M.


    In addition to the commonly observed single molecule fluorescence intensity fluctuations due to molecular reorientation dynamics, a perylene bisimide-calixarene compound (1) shows additional on-off fluctuations due to its ability to undergo intramolecular excited state electron transfer (PET). This

  9. Polymer glass transitions switch electron transfer in individual molecules

    NARCIS (Netherlands)

    Siekierzycka, J.R.; Hippius, C.; Würthner, F.; Williams, R.M.; Brouwer, A.M.


    Essentially complete photoinduced electron transfer quenching of the fluorescence of a perylene−calixarene compound occurs in poly(methyl acrylate) and poly(vinyl acetate) above their glass transition temperatures (T-g), but the fluorescence is completely recovered upon cooling the polymer matrix to

  10. Synthesis of phosphorylated calix[4]arene derivatives for the design of solid phases immobilizing uranyl cations

    Energy Technology Data Exchange (ETDEWEB)

    Maroun, E.B.; Hagege, A.; Asfari, Z. [Laboratoire de Chimie Analytique et Minerale, UMR 7178 ULP/CNRS/IN2P3 LC4, ECPM, Strasbourg Cedex (France); Basset, CH.; Quemeneur, E.; Vidaud, C. [CEA IBEB, SBTN, Centre de Marcoule, Bagnols-sur-Ceze (France)


    With the aim of developing supports for uranyl cations immobilisation, new 1, 3-alternate calix[4]arenes bearing both phosphonic acid functions as chelating sites and N-succinimide-4-oxa-butyrate as the anchoring arm were synthesised in good yields. The coupling of such calixarenes to a gel was performed and a successful immobilisation of uranyl cations was obtained. (authors)

  11. Calix[4]arene supported clusters: a dimer of [Mn(III)Mn(II)] dimers

    DEFF Research Database (Denmark)

    Taylor, Stephanie M; McIntosh, Ruaraidh D; Beavers, Christine M;


    Phosphinate ligands allow for the transformation of a calix[4]arene supported [Mn(III)(2)Mn(II)(2)] tetramer cluster motif into an unusual [Mn(III)Mn(II)](2) dimer of dimers; the clusters self-assemble in the crystal to form bi-layer arrays reminiscent of the typical packing of calixarene solvates....

  12. Synthesis and Cation Complexation of Lariat Calix[4 ] crowns

    Institute of Scientific and Technical Information of China (English)

    SHI Zheng-Wei; JIN Chuan-Ming; LU Guo-Yuan


    @@ Calixcrowns carrying bridging polyethyleneoxy moieties on the lower rim, which combine calixarene and crown ether in a single molecule, are a novel class of host compounds which have attracted increasing attention because of their increased ability for selective complexation of cations and neutral molecules compared with crown ethers or cal ixarenes.

  13. An Inherent Chiral Calix[4]arene Bearing Chiral Groups without Forming Sub-ring

    Institute of Scientific and Technical Information of China (English)

    Xian Xian LIU; Yan Song ZHENG; Wan Ling MO


    The NMR spectra revealed that the calixarene frame of 1, 3-disubstituted calix[4]arenes bearing optically active groups is asymmetric, even without the formation of a sub-ring. This inherent chirality arises from the interaction of the two chiral groups, which hinder the substituents' free rotation. Thus, these chiral calix[4]arenes display good chiral recognition ability.

  14. Self-assembly of amphiphilic anionic calix[4]arenes and encapsulation of poorly soluble naproxen and flurbiprofen. (United States)

    Barbera, Lucia; Gattuso, Giuseppe; Kohnke, Franz H; Notti, Anna; Pappalardo, Sebastiano; Parisi, Melchiorre F; Pisagatti, Ilenia; Patanè, Salvatore; Micali, Norberto; Villari, Valentina


    Supramolecular aggregates formed through the association of an amphiphilic tetra-O-butylsulfonate calix[4]arene 1 were investigated in aqueous solution by a combination of different techniques (NMR, DLS and AFM). The ability of the micellar aggregates of calixarene 1 to increase the solubility of poorly water-soluble drugs was studied.

  15. Calix[4]arene Polyaza Derivatives: Novel Effective Neutral Receptors for Cations and (a)-Amino Acids

    Institute of Scientific and Technical Information of China (English)


    @@ Introduction Calixarenes are one of the most important supramolecular building blocks, which can be modified by introducing different functional and/or structrual groups to create a specific interaction between the host and the target molecules, such as metal cations and small organic molecules[1,2]. In particular, the recognition of amino acids is an interesting theme in biomimetic chemistry[3].

  16. Progress in the studies of electrochemically controllable host-guest interactions

    Institute of Scientific and Technical Information of China (English)

    LIU Jing; LI Yuangang; FANG Yu


    Studies on the electrochemically controllable host-guest interactions have received considerable attention since the middle of the 1980s. In this paper, progress in such studies is reviewed according to the types of the hosts, including cyclodextrin, calixarene,cucurbituril, cyclophane, and so on. In addition, perspectives for the future development and potential applications of the interactions are discussed.

  17. An Approach to Monocrowned Tiacalixarene

    Institute of Scientific and Technical Information of China (English)

    JIN,Yan; GONG,Shu-Ling; CHEN,Yuan-Yin


    @@ Thiacalixarenes are macrocycles comprising phenolic units connected in the ortho position by sulfur bridges instead of the methylene bridges of calixarenes.[1] When thiacalixarene was bridged with polyoxyethylene segments, thiacalixcrowns or crowned thiacalixarenes were constructed. Up to date, some thiacalix[4]biscrowns as well as a few thiacalix[4]monocrowns have been reported.

  18. Separation of uranium from aqueous solutions using calix[6]arenes in liquid-liquid extraction as well as solid phase extraction; Abtrennung von Uran aus waessriger Loesung durch Calix[6]arene mittels Fluessig-Fluessig-Extraktion sowie Festphasen-Extraktion

    Energy Technology Data Exchange (ETDEWEB)

    Schmeide, K.; Geipel, G.; Bernhard, G.


    The suitability of different calyx[n] arene types for uranyl extraction from liquid solutions was examined by means of liquid-liquid extraction using aqueous phases and organic solvents of varying compositions. It was found that COOH-derivatised calyx[6] arenes have good extraction properties and can even be used in the acid pH range. The use of calixarene-modified fleeces for the separation of uranyl from aqueous phases was examined in batch experiments with pH and uranyl concentration as variables and in the presence or absence of competing ions. The results showed that calixarene-modified fleeces can be used for uranium separation starting from pH 4. At pH 5, up to a maximum of 7.6 x 10{sup -7} mol uranium can be bound per 1 g of calixarene-modified fleece. The separation of uranyl from synthetic pit waters was examined as a means of testing the separation capacity of calixarene-modified fleeces in environmentally sensitive waters. Studies on the reversibility of uranium bonding to calixarene-treated polyester fleeces have shown that under environmentally realistic conditions (neutral pH range) the uranium is firmly bound to the calixarene-modified fleeces and cannot be mobilised. By contrast, in acidic environments calixarene-modified fleeces are capable of near-complete regeneration. Such regenerated textile filter materials can then be used for further uranium separation cycles. [German] Die Eignung verschiedener Calix[n]aren-Typen fuer die Uranylextraktion aus waessriger Loesung wurde mittels Fluessig-Fluessig-Extraktion unter Variation der Zusammensetzung der waessrigen Phase und des organischen Loesungsmittels untersucht. Es konnte gezeigt werden, dass COOH-derivatisierte Calix[6]arene gute Extraktionseigenschaften aufweisen und selbst im sauren pH-Bereich angewendet werden koennen. Die Uranylabtrennung aus waessriger Loesung durch calixarenmodifizierte Vliese wurde in Abhaengigkeit des pH-Wertes und der Uranylkonzentration in Abwesenheit und Gegenwart von

  19. Extraction and separation of thorium and rare earths with 5,11,17,23-tetra (diethoxyphosphoryl)-25,26,27,28-tetraacetoxycalix [4] arene

    Institute of Scientific and Technical Information of China (English)

    LI Yanling; LU Youcai; BAI Yan; LIAO Wuping


    A calixarene derivative,5,11,17,23-tetra(diethoxyphosphoryl)-25,26,27,28-tetraacetoxycalix[4]arene (L),was studied for the extraction and separation of thorium and rare earths in nitrate medium.Thorium was extracted into the organic phase by a complex of Th(NO3)4·L with the logarithm of the equilibrium constant of 2.77.Thermodynamic functions,△H,△G and △S were calculated to be -2.49,-15.55 kJ/mol and 44.53 J/(mol·K),respectively.The results indicated that this calixarene derivative might be used to separate thorium from rare earths and the separation factors were larger than 26.However,the salting-out agents affected the separation.

  20. Clicked and long spaced galactosyl- and lactosylcalix[4]arenes: new multivalent galectin-3 ligands

    Directory of Open Access Journals (Sweden)

    Silvia Bernardi


    Full Text Available Four novel calix[4]arene-based glycoclusters were synthesized by conjugating the saccharide units to the macrocyclic scaffold using the CuAAC reaction and using long and hydrophilic ethylene glycol spacers. Initially, two galactosylcalix[4]arenes were prepared starting from saccharide units and calixarene cores which differ in the relative dispositions of the alkyne and azido groups. Once the most convenient synthetic pathway was selected, two further lactosylcalix[4]arenes were obtained, one in the cone, the other one in the 1,3-alternate structure. Preliminary studies of the interactions of these novel glycocalixarenes with galectin-3 were carried out by using a lectin-functionalized chip and surface plasmon resonance. These studies indicate a higher affinity of lactosyl- over galactosylcalixarenes. Furthermore, we confirmed that in case of this specific lectin binding the presentation of lactose units on a cone calixarene is highly preferred with respect to its isomeric form in the 1,3-alternate structure.

  1. Investigation of the mechanism of formation of overbased detergents

    CERN Document Server

    Courtois, J P


    This thesis describes an experimental study of calixarate overbased detergent oil additives, used to neutralise acidic by-products of engine combustion. Aspects of interest in this study include experimental synthesis of calixarenes and overbased detergents, physical and structural characterisation and monitoring of the synthesis process. Two types of calixarenes were prepared (6 and 8 phenolic units). A synthesis procedure of the calixarate overbased detergent was set up, based on adaptation of existing procedures used for other classes of overbased detergents. The procedure was also modified to suit a lab-scale. sup 1 sup 3 C NMR and UV-Vis spectroscopy have provided strong evidence for a precursor of the overbased detergent. The ionisation of the surfactants (stearic acid carboxylic group, and phenolic units) was clearly established. The synthesis process was monitored at the molecular and macroscopic level. The use of sup 1 sup 3 C-labelled compounds enabled a semi-quantitative study of the concentration ...

  2. Detoxification of VX and Other V‐Type Nerve Agents in Water at 37 °C and pH 7.4 by Substituted Sulfonatocalix[4]arenes (United States)

    Schneider, Christian; Bierwisch, Anne; Koller, Marianne; Worek, Franz


    Abstract Sulfonatocalix[4]arenes with an appended hydroxamic acid residue can detoxify VX and related V‐type neurotoxic organophosphonates with half‐lives down to 3 min in aqueous buffer at 37 °C and pH 7.4. The detoxification activity is attributed to the millimolar affinity of the calixarene moiety for the positively charged organophosphonates in combination with the correct arrangement of the hydroxamic acid group. The reaction involves phosphonylation of the hydroxamic acid followed by a Lossen rearrangement, thus rendering the mode of action stoichiometric rather than catalytic. Nevertheless, these calixarenes are currently the most efficient low‐molecular‐weight compounds for detoxifying persistent V‐type nerve agents under mild conditions. They thus represent lead structures for novel antidotes that allow treatment of poisonings by these highly toxic chemicals. PMID:27627873

  3. Uranyl complexes formed with a para-t-butylcalix[4]arene bearing phosphinoyl pendant arms on the lower rim. Solid and solution studies

    Energy Technology Data Exchange (ETDEWEB)

    Ramirez, F. de M. [Instituto Nacional de Investigaciones Nucleares, La Marquesa, Ocoyoacac (Mexico). Dept. de Quimica; Varbanov, S. [Bulgarian Academy of Sciences, Sofia (Bulgaria). Inst. of Organic Chemistry with Center of Phytochemistry; Buenzli, J.C.G. [Ecole Polytechnique Federale de Lausanne (EPFL) (Switzerland). Inst. of Chemical Sciences and Engineering; Rivas-Silva, J.F.; Ocana-Bribiesca, M.A. [Instituto de Fisica de la BUAP, Puebla (Mexico); Cortes-Jacome, M.A.; Toledo-Antonio, J.A. [Instituto Mexicano del Petroleo/Programa de Ingenieria Molecular (Mexico)


    The current interest in functionalized calixarenes with phosphorylated pendant arms resides in their coordination ability towards f elements and capability towards actinide/rare earth separation. Uranyl cation forms 1:1 and 1:2 (M:L) complexes with a tetra-phosphinoylated p-tert-butylcalix[4]arene, B{sub 4}bL{sup 4}: UO{sub 2}(NO{sub 3}){sub 2}(B{sub 4}bL{sup 4}){sub n} . xH{sub 2}O (n = 1, x = 2, 1; n = 2, x = 6, 2). Spectroscopic data point to the inner coordination sphere of 1 containing one monodentate nitrate anion, one water molecule and the four phosphinoylated arms bound to UO{sub 2}{sup 2+} while in 2, uranyl is only coordinated to calixarene ligands. In both cases the U(VI) ion is 8-coordinate. Uranyl complexes display enhanced metal-centred luminescence due to energy transfer from the calixarene ligands; the luminescence decays are bi-exponential with associated lifetimes in the ranges 220 {mu}s < {tau}{sub s} < 250 {mu}s and 630 {mu}s < {tau}{sub L} < 640 {mu}s, pointing to the presence of two species with differently coordinated calixarene, as substantiated by a XPS study of U(4f{sub 5/2,7/2}), O(1s) and P(2p) levels on solid state samples. The extraction study of UO{sub 2}{sup 2+} cation and trivalent rare-earth (Y, La, Eu) ions from acidic nitrate media by B{sub 4}bL{sup 4} in chloroform shows the uranyl cation being much more extracted than rare earths. (orig.)

  4. The Synthesis of a New Type of Calix[4]arene with Chiral Pendant

    Institute of Scientific and Technical Information of China (English)


    Two new chiral calixarenes were synthesized by condensing 1,3-bis-chlorocarbomethyl-calix[4]arehes with (1S, 2S)-2-amino-1-(4-nitrophenyl)-1, 3-propanediol, a by-product from antibiotic industry ,and were characterized by 1H-NMR , MS-FAB, and elemental analysis. The 1H-NMR spectra show that those molecules assume a cone conformation in solution.

  5. 2-(4-Bromobenzyl-5,11,17,23-tetra-tert-butyl-25,26,27,28-tetramethoxycalix[4]arene

    Directory of Open Access Journals (Sweden)

    Conrad Fischer


    Full Text Available In the title compound, C55H69BrO4, the calixarene molecule displays a `partial cone' conformation bearing the lateral substituent in a sterically favorable equatorial arrangement between two syn-orientated arene units. The crystal packing is stabilized by weak C—H...π contacts, involving one tert-butyl group, and π–stacking interactions of the lateral bromobenzene units [centroid–centroid distance = 3.706 (1 Å].

  6. Enantiopure inherently chiral calix[4]arene derivatives containing quinolin-2-yl-methanol moiety:Synthesis and application in the catalytic asymmetric addition of diethylzinc to benzaldehyde

    Institute of Scientific and Technical Information of China (English)


    A series of novel N,O-type chiral ligands derived from enantiopure inherently chiral calix[4]arenes containing quinolin-2-yl-methanol moiety in the cone or partialcone conformation have been synthe-sized and characterized. Moreover,they have been applied to the catalytic asymmetric addition of diethylzinc to benzaldehyde,which represents the first example that the inherently chiral calixarene can be used as the chiral ligands for the catalytic asymmetric synthesis.

  7. First synthesis of a '1,2-diquinone-calix[4]arene'. Interaction of its reduced form with Ag+


    Vataj, Rame; Ridaoui, Hassan; Louati, Alain; Gabelica, Valérie; Steyer, Stéphane; MATT, DOMINIQUE


    Electrochemical oxidation of 5,11,17,23-tetra-tert-butyl-25,26-bis(diphenylphosphinoylmethoxy)-27,28-dihydroxycalix[4]arene (3), a calixarene with two phosphoryl units appended on proximal positions, affords the corresponding '1,2-diquinonecalix[4]arene' (4). The formation of 4 results from nucleophilic attack of residual water on anodically generated diphenoxylium. cations. Preliminary voltammetric experiments in CH3CN on a platinum electrode showed that 4 is suitable for electrochemical det...

  8. Synthesis of Ag nanoparticles for the electrochemical detection of anticancer drug flutamide

    Institute of Scientific and Technical Information of China (English)

    Farzaneh Ahmadi; Jahan Bakhsh Raoof; Reza Ojani; Mehdi Baghayeri; Moslem Mansour Lakouraj; Hamed Tashakkorian


    Ag nanoparticles were synthesized on the surface of a glassy carbon electrode modified with p‐tert‐butylcalix[4]arene and p‐tert‐butylcalix[6]arene by the deposition of Ag+at an open circuit potential followed by the electrochemical reduction of the Ag+. The presence of the calixarene layer on the electrode surface controlled the particle size and prevented agglomeration. Cyclic voltam‐metry showed that the Ag nanoparticles on the modified glassy carbon electrode had good catalytic ability for the reduction of flutamide. The effects of calixarene concentration, potential applied for the reduction of Ag+, number of calixarene layers, and pH value on the electrocatalytic activity of the Ag nanoparticles were investigated. The modified electrode had a linear range in differential pulse voltammetry of 10−1000 µmol/L with a detection limit of 9.33 µmol/L for flutamide at an S/N=3. The method was applied to the detection of flutamide in practical samples.

  9. Solid-phase Microextraction with Benzoxy-calix[6]arene Fiber Coupled to Gas Chromatography for the Analysis of Polycyclic Aromatic Hydrocarbons in Water

    Institute of Scientific and Technical Information of China (English)

    YE Chang-wen; ZHANG Xue-na; HUANG Jiang-yan; LI Xiu-juan; PAN Si-yi


    Headspace solid-phase microextraction(HS-SPME) with sol-gel calix[6]arene-containing fiber followed by gas chromatography with a flame ionization detector was used to examine the composition and distribution of seven polycyclic aromatic hydrocarbons(PAHs) in water. The novel SPME fiber exhibited higher extraction efficien cy to PAHs compared with poly(dimethylsiloxane) and other calixarene-containing fibers. Extraction/retention me chanism based on the interactions between calixarenes and PAHs was discussed. Owing to the good selectivity and high extraction capability of this calixarene fiber, low detection limits were obtained in a range of 0.34—6.50 ng/L and the relative standard deviation values were ≤ 12.3% for all of the analytes. The linear ranges of the proposed method were five orders of magnitude for the tested compounds, with linear correlation coefficients(r) greater than 0.998. The method was applied to the determination of polycyclic aromatic hydrocarbons in nine water sources in Wuhan City, China. Standard addition method was selected for the quantification and the recovery values were in a satisfactory range. Total PAHs concentrations in the nine surface water samples were found to vary between unde tectable and 8.840 μg/L with two-and three-ring PAHs predominating.

  10. Sulphonic acid derivatives as probes of pore properties of volume-regulated anion channels in endothelial cells. (United States)

    Droogmans, G; Maertens, C; Prenen, J; Nilius, B


    1. We have used the whole-cell patch-clamp technique to study the effects of 4-sulphonic-calixarenes and some other poly-sulphonic acid agents, such as suramin and basilen blue, on volume-regulated anion channel (VRAC) currents in cultured endothelial cells (CPAE cells). 2. The 4-sulphonic-calixarenes induced a fast inhibition at positive potentials but were ineffective at negative potentials. At small positive potentials, 4-sulphonic-calix[4]arene was a more effective inhibitor than 4-sulphonic-calix[6]arene and -calix[8]arene, which became more effective at more positive potentials. 3. Also suramin and basilen blue induced a voltage dependent current inhibition, reaching a maximum around +40 mV and declining at more positive potentials. 4. The voltage dependence of inhibition was modelled by assuming that these negatively charged molecules bind to a site inside VRAC that senses a fraction delta of the applied electrical field, ranging beween 0.16 to 0.32. 4-Sulphonic-calix[4]arene, suramin and basilen blue bind and occlude VRAC at moderate potentials, but permeate the channel at more positive potentials. 4-Sulphonic-calix[6]arene and -calix[8]arene however do not permeate the channel. From the structural information of the calixarenes, we estimate a lower and upper limit of 11*12 and 17*12 A2 respectively for the cross-sectional area of the pore.

  11. Binding of DNA by a dinitro-diester calix[4]arene: denaturation and condensation of DNA. (United States)

    Ostos, F J; Lebron, J A; Moyá, M L; Deasy, M; López-Cornejo, P


    A study of a dinitro-diester calix[4]arene (5,17-(3-nitrobenzylideneamino)-11,23-di-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene) interaction with calf-thymus DNA was carried out using several techniques. The measurements were done at various molar ratios X=[calixarene]/[DNA]. Results show diverse changes in the DNA conformation depending on the X value. Thus, at low macrocycle concentrations, the calixarene binds to the polynucleotide. This interaction, mainly in groove mode, weakens the hydrogen bonds between base pairs of the helix inducing denaturation of the double strands, as well as condensation of the macromolecule, from an extended coil state to a globular state. An opposite effect is observed at X molar ratios higher than 0.07. The de-condensation of DNA happens, that is, the transition from a compact state to a more extended conformation, probably due to the stacking of calixarene molecules in the solution. Results also show the importance of making a proper choice of the system under consideration.

  12. Synthesis and evaluation of a new colorimetric and ratiometric fluorescence probe for copper ions

    Energy Technology Data Exchange (ETDEWEB)

    Chawla, Har Mohindra, E-mail:; Munjal, Priyanka; Goel, Preeti


    Synthesis and spectroscopic evaluation of compounds 3a, 3b and 4 reveal that cone conformer of 25,27-bis(o-aminothiophenyl propyloxy) -tetra-p-tert-butylcalix[4]arene 3a can function as a highly selective ratiometric and colorimetric fluorescence probe for copper ions. - Highlights: • We have synthesized a new calixarene based receptor 3 for Cu{sup 2+}. • 3 Showed ratiometric changes with Cu{sup 2+} in emission spectrum. • Reference compound 4 showed quenching with Cu{sup 2+} in emission spectrum. • Importance of calix[4]arene platform in ion recognition.

  13. Calix[6]azacryptand Ligand with a Sterically Protected Tren-Based Coordination Site for Metal Ions. (United States)

    Zahim, Sara; Wickramasinghe, Lasantha A; Evano, Gwilherm; Jabin, Ivan; Schrock, Richard R; Müller, Peter


    A new calix[6]azacryptand ligand has been prepared in six steps starting from 1,3,5-trismethoxycalix[6]arene. An X-ray study shows that this ligand has a sterically protected tren-based binding site at the bottom of a polyaromatic bowl and ether sites around its rim. It binds Zn(2+) to give a complex in which zinc is in a trigonal bipyramidal geometry with a water bound in one apical position and two additional hydrogen-bonded waters that fill the calixarene cavity.

  14. Host-guest supramolecular nanosystems for cancer diagnostics and therapeutics. (United States)

    Wang, Lei; Li, Li-li; Fan, Yun-shan; Wang, Hao


    Extensive efforts have been devoted to the construction of functional supramolecular nanosystems for applications in catalysis, energy conversion, sensing and biomedicine. The applications of supramolecular nanosystems such as liposomes, micelles, inorganic nanoparticles, carbon materials for cancer diagnostics and therapeutics have been reviewed by other groups. Here, we will focus on the recent momentous advances in the implementation of typical supramolecular hosts (i.e., cyclodextrins, calixarenes, cucurbiturils and metallo-hosts) and their nanosystems in cancer diagnostics and therapeutics. We discuss the evolutive process of supramolecular nanosystems from the structural control and characterization to their diagnostic and therapeutic function exploitation and even the future potentials for clinical translation.

  15. Synthesis and cationic selectivity studies of novel calix[4]arene derivatives containing heteroatom at the lower rim

    Institute of Scientific and Technical Information of China (English)

    WANG; Hao; LI; Zhe; LIU; Yu


    A series of calixarene derivatives 2-5 containing heteroatom at the lower rim have been synthesized. 1H NMR studies and crystallographic structures demonstrated that the calix[4]arene derivatives adopted cone conformations. Their cationic binding abilities and selectivities towards heavy and transition metal ions have been evaluated by solvent extraction of aqueous metal picrates. The obtained results indicated that the introduction of nitrogen, sulfur, and/or phosphor atoms to the calix[4]arene framework could effectively enhance their binding ability and selectivity for heavy and transition metal ions, such as Pb2+ or Ag+.

  16. Mechanochemical organic synthesis. (United States)

    Wang, Guan-Wu


    Recently, mechanical milling using a mixer mill or planetary mill has been fruitfully utilized in organic synthesis under solvent-free conditions. This review article provides a comprehensive overview of various solvent-free mechanochemical organic reactions, including metal-mediated or -catalyzed reactions, condensation reactions, nucleophilic additions, cascade reactions, Diels-Alder reactions, oxidations, reductions, halogenation/aminohalogenation, etc. The ball milling technique has also been applied to the synthesis of calixarenes, rotaxanes and cage compounds, asymmetric synthesis as well as the transformation of biologically active compounds.

  17. Synthesis and assembly of self-complementary calix[4]arenes. (United States)

    Shimizu, K D; Rebek, J


    A calix[4]arene was designed to reversibly dimerize and form an egg-shaped enclosure. Adhesive interactions in the assembly were provided by four self-associating ureas, which form a cyclic array containing 16 hydrogen bonds. The synthesis was completed in four steps from the previously described O,O',O",O"'-tetrabenzylcalix[4]arene. Evidence for dimerization of the calixarene tetraurea was provided by H NMR, mass spectrometry, and the observation of encapsulated molecules. The resulting cavity was of sufficient size to capture guests such as ethyl benzene and p-xylene. Images Fig. 1 Fig. 2 Fig. 6 PMID:8618910

  18. Hybrid liposomal PEGylated calix[4]arene systems as drug delivery platforms for curcumin. (United States)

    Drakalska, Elena; Momekova, Denitsa; Manolova, Yana; Budurova, Dessislava; Momekov, Georgi; Genova, Margarita; Antonov, Liudmil; Lambov, Nikolay; Rangelov, Stanislav


    The tremendous therapeutic potential of curcumin as a chemopreventive, antineoplastic and chemosensitizing agent has failed to progress towards clinical development and commercialization due to its unfavorable physicochemical properties, low aqueous solubility, chemical instability, and pharmacokinetics. The present contribution is focused on the feasibility of using PEGylated calixarene, in particular polyoxyethylene-derivatized tert-butylcalix[4]arene, to prepare various platforms for delivery of curcumin such as inclusion complex, supramolecular aggregates, and hybrid liposomal systems. The inclusion complex is characterized by UV-vis and FT-IR spectroscopy as well as thermal gravimetrical analysis and differential scanning calorimetry. At concentrations exceeding the critical micellization concentration of PEGylated calixarene, the tremendous solubility enhancement of curcumin is attributed to additional solubilization and hydrophobic non-covalent interactions of the drug with supramolecular aggregates. A hybrid liposomal system is created via encapsulation of the inclusion complex in dipalmitoylphosphatidylcholine:cholesterol liposomes. Bare and liposomal curcumin:BEC-X inclusion complexes, as well as free curcumin were additionally investigated for cytotoxicity and apoptogenic activity against human tumor cell lines.

  19. Interaction between Langmuir and Langmuir-Blodgett films of two calix[4]arenes with aqueous copper and lithium ions. (United States)

    Supian, Faridah L; Richardson, Tim H; Deasy, Mary; Kelleher, Fintan; Ward, James P; McKee, Vickie


    The binding interactions between aqueous copper (Cu(2+)) and lithium (Li(+)) ions and Langmuir monolayers and Langmuir-Blodgett (LB) multilayers have been investigated by studying surface pressure-area (Pi-A) isotherms and surface potential-area (DeltaV-A) behavior in order to find the effective dipole moment, mu(perpendicular), of the calixarene molecules in the uncomplexed and complexed states. The orientation of both calix[4]arenes, namely, 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene and 5,17-(9H-fluoren-2-yl)methyleneamino)-11,23-di-tert-butyl-25,27-diethoxycarbonyl methyleneoxy-26,28-dihydroxycalix[4]arene, is such that the plane of the calix ring is parallel with the plane of the water surface regardless of the ion content of the subphase. The Gibbs equation was used to interpret the adsorption of ions with both calix[4]arenes as a function of the concentration. Effective dipole moments have been calculated from surface potential values using the Helmholtz equation. In this work, new LB films have been prepared employing two novel amphiphilic calix[4]arene derivatives bearing different upper rim substituents. Thus, the effect of modifiying the upper rim has been observed. The results have shown that these calixarenes may be useful components of ion sensors.

  20. Interaction of bolaform surfactants with p-sulfonatocalix[4]arene: the role of two positive charges in the binding. (United States)

    Francisco, Vitor; Garcia-Rio, Luis


    The inclusion binding manners of bolaform surfactants of type C(n)R6(2+) 2Br(-) with different spacer lengths (n = 6, 12) and terminal headgroup volumes (R = methyl, ethyl) by p-sulfonatocalix[4]arene were studied. The combination of ITC parameters (binding constants and complexation enthalpy and entropy) and NMR chemical shifts and NOE cross-peaks obtained upon complexation allows us to propose different binding modes. The results point out that the spacer length has an influence on the binding stoichiometry. The bolaforms with larger spacer lengths between polar head groups enable the formation of 2:1 complexes in addition to 1:1, while with the shorter spacer they form only 1:1 complexes. On the other hand, the formation of 1:1 complexes is not affected by the headgroup volume or the spacer length of the bolaform. Unexpectedly, a complex binding mode was observed where both positive charged terminal groups of the bolaform are accommodated in the cavity of the calixarene. The inclusion of both terminal groups of the guests can be related to its own structure but also evidence the high flexibility of the calixarene.

  1. Thermal decomposition mechanism of p-tert-butyl-calix[n]arenes

    Energy Technology Data Exchange (ETDEWEB)

    Chennakesavulu, K., E-mail: [National Metallurgical Laboratory Madras Centre, CSIR Madras Complex, Taramani, Chennai 600 113 (India); Department of Chemistry, Sathyabama University, Jeppiaar Nagar, Chennai 600 119 (India); Sreedevi, P.; Raviathul Basaria, M. [National Metallurgical Laboratory Madras Centre, CSIR Madras Complex, Taramani, Chennai 600 113 (India); Ramanjaneya Reddy, G. [Department of Inorganic Chemistry, Guindy Campus, University of Madras, Chennai 600 025 (India); Sasipraba, T. [International Research Centre, Sathyabama University, Jeppiaar Nagar, Chennai 600 119 (India); Bhaskar Raju, G.; Prabhakar, S. [National Metallurgical Laboratory Madras Centre, CSIR Madras Complex, Taramani, Chennai 600 113 (India)


    Highlights: • Systematic thermal decomposition, structural elucidation of intermediates at various quenched temperatures. • At solid state the phenolic free radical was quenched and was evidenced by recording stable EPR. • Since the lower decomposition energy these p-tert-butyl-calix[n]arenes can be used as a antioxidants for thermal stabilization of polyolefins. • Solid state NMR CP-MAS studies show the breakage of calixarene at bridged methylene. • Kinetic triplets of p-tert-butyl-calixarenes were determined by model free methods. - Abstract: Thermal decomposition of p-tert-butyl-calix[n]arene was studied using thermo gravimetry (TG) and differential thermo gram (DTG) methods. Non-isothermal TG was done under static air atmosphere with 1, 2.5, 5.0 and 10.0 K/min. Model-free methods such as Friedman and Flynn Wall Ozawa (FWO) were used to evaluate the kinetic parameters such as activation energy and exponential factors. The probable thermal decomposition mechanism was proposed by analyzing the quenched intermediate p-tert-butyl-calix[n]arene samples with FTIR, mass, {sup 1}H NMR, {sup 13}C NMR cross polarization magic angle spectrometry (CP-MAS), EPR spectroscopy and elemental analysis. The thermal stability of the polyolefins was checked with p-tert-butyl-calix[n]arene as an antioxidant additive.

  2. Electrochemical synthesis of Ag nanoparticles supported on glassy carbon electrode by means of p-isopropyl calix[6]arene matrix and its application for electrocatalytic reduction of H{sub 2}O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Raoof, Jahan Bakhsh, E-mail: [Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, Mazandaran University, 3rd Kilometer of Air Force Road, 47416-95447 Babolsar (Iran, Islamic Republic of); Ojani, Reza; Hasheminejad, Ehteram [Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, Mazandaran University, 3rd Kilometer of Air Force Road, 47416-95447 Babolsar (Iran, Islamic Republic of); Rashid-Nadimi, Sahar [Department of Renewable Energy, Faculty of Advanced Science and Technology, University of Isfahan, 81746-73441 Isfahan (Iran, Islamic Republic of)


    The silver nanoparticles were prepared on the glassy carbon (GC) electrode, modified with p-iso propyl calix[6]arene, by preconcentration of silver ions in open circuit potential and followed by electrochemical reduction of silver ions. The stepwise fabrication process of Ag nanoparticles was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. The prepared Ag nanoparticles were deposited with an average size of 70 nm and a homogeneous distribution on the surface of electrode. The observed results indicated that the presence of calixarene layer on the electrode surface can control the particle size and prevent the agglomeratione and electrochemical deposition is a promising technique for preparation of nanoparticles due to its easy-to-use procedure and low cost of implementation. Cyclic voltammetry experiments showed that Ag nanoparticles had a good catalytic ability for the reduction of hydrogen peroxide (H{sub 2}O{sub 2}). The effects of p-isopropyl calix[6]arene concentration, applied potential for reduction of Ag{sup +}, number of calixarene layers and pH value on the electrocatalytic ability of Ag nanoparticles were investigated. The present modified electrode exhibited a linear range from 5.0 Multiplication-Sign 10{sup -5} to 6.5 Multiplication-Sign 10{sup -3} M and a detection limit 2.7 Multiplication-Sign 10{sup -5} M of H{sub 2}O{sub 2} (S/N = 3) using amperometric method.

  3. Determination of Dioxins in Blood Using Nano-baskets Doped in Emulsion Liquid Membranes

    Institute of Scientific and Technical Information of China (English)



    Extraction of dioxins from blood samples was carried out by inclusion-facilitated emulsion liquid membrane process.The novelty of this work is the application of nano-baskets of calixarene and emulsion liquid membranes in the selective and efficient preconcentration of dioxin.For this aim,four derivatives ofp-tert-calix[4]arene bearing different sulfonamide moieties were synthesized and their inclusion-extraction parameters were optimized including the calixarene's scaffold and concentration(as the carrier/demulsifier),the diluent type in membrane,the phase and the treat ratio,mixing speed,and initial solute concentration.Determinations were followed by a gas chromatograph and the results reveal that under the optimized operating conditions,the preconcentration of dioxins was improved and the method achieved lower limit of detections(LODs).Under optimal conditions,the figures of merits were determined to be LOD 1.0 pg/L,dynamic range 0.6-112.0 pg/L,RSD 5.5%(n=5),and the maximum enrichment factor and recovery were determined to be 3.3 and 99%,respectively.

  4. Amino acids separation with the tetracarboxylic derived of the para-ter-butylcalix[4]arene by means of solid-liquid extraction assisted with lanthanides; Separacion de aminoacidos con el derivado tetracarboxilico del para-ter-butilcalix[4]areno mediante extraccion solido-liquido asistida con lantanidos

    Energy Technology Data Exchange (ETDEWEB)

    Bernal R, R. del C.


    The tetracarboxylic derived of the para-ter-butylcalix[4]arene (B{sub 4}ACEbL{sup 4}) does not exist commercially for what was synthesized and characterized at laboratory level. The separation of the L-tyrosine amino acid was studied by means of a solid-liquid extraction system with the B{sub 4}ACEbL{sup 4} as solid phase, in function of ph (2.5-7.5) and contact time (5 and 15 hours) to temperature of 15-17 grades C. Resulted that the ph and the contact time were decisive in the extraction percentage of water tyrosine. The lowest percentage was 49% to ph 4 and the highest percentage was 61% to ph 7.5 with 15 hours of contact. In a contact time of 5 hours the extraction was inferior to 32% (ph 4) and of 47% to ph 6.5. The europium effect (Eu (III)) was studied to ph acid in the tyrosine separation and was found that the tyrosine extraction is not increased neither decomposes in europium presence, this is simultaneously extracted by the calixarene but it does not enter in competition for the calixarene with the amino acid. The separate solid phases: calixarene-tyrosine was analyzed by Far infrared radiation (Fir), Mid-Infrared (Mir) spectroscopy and luminescence to check the tyrosine presence in the separate solids as well as the nature of the connection calixarene-tyrosine. In this way was possible to check the tyrosine presence and to propose the formed molecular species tyrosine-calixarene, those which interact mainly by means of hydrogen connections and Van der Waals forces. The liquid phases before and after the extraction were analyzed by UV-Vis spectrophotometry and luminescence. The Neutron activation analysis was used to determine the europium content in the solid and liquid phases of extractions in europium presence. The tyrosine degradation also shows dependence with the ph, obtaining 88% degradation to the 24 hours to ph 7.5, while to ph 3 is degraded the 54% of tyrosine present in the sample. The europium presence does not affect the tyrosine extraction

  5. Selective extraction of cesium: from compound to process; Extraction selective du cesium: de la molecule au procede

    Energy Technology Data Exchange (ETDEWEB)

    Simon, N.; Eymard, S.; Tournois, B.; Dozol, J.F. [CEA Cadarache, Dept. d' Entreposage et de Stockage des Dechets (DCC/DESD/SEP), 13 - Saint-Paul-lez-Durance (France)


    Under the French law of 30 December 1991 on nuclear waste management, research is conducted to recover long-lived fission products from high-level radioactive effluents generated by spent fuel reprocessing, in order to destroy them by transmutation or encapsulate them in specific matrices. Cesium extraction with mono and bis-crown calix(4)arenes (Frame 1) is a candidate for process development. These extractants remove cesium from highly acidic or basic pH media even with high salinity. A real raffinate was treated in 1994 in a hot cell to extract cesium with a calix-crown extractant. The success of this one batch experiment confirmed the feasibility of cesium decontamination from high-level liquid waste. It was then decided to develop a process flowchart to extract cesium selectively from high-level raffinate, to be included in the general scheme of long-lived radionuclide partitioning. It was accordingly decided to develop a process based on liquid-liquid extraction and hence optimize a calixarene/diluent solvent according to: - hydraulic properties: density, viscosity, interfacial tension, - chemical criteria: sufficient cesium extraction (depending on the diluent), kinetics, third phase elimination... New mono-crown-calixarenes branched with long aliphatic groups (Frame 2) were designed to be soluble in aliphatic diluents. To prevent third phase formation associated with nitric acid extraction, the addition of modifiers (alcohol, phosphate and amide) in the organic phase was tested (Frame 3). Table 1 shows examples of calixarene/diluent systems suitable for a process flowchart, and Figure 2 provides data on cesium extraction with these new systems. Alongside these improvements, a system based on a modified 1,3-di(n-octyl-oxy)2,4-calix[4]arene crown and a modified diluent was also developed, considering a mixed TPH/NPHE system as the diluent, where TPH (hydrogenated tetra propylene) is a common aliphatic industrial solvent and NPHE is nitrophenyl

  6. Demonstration of Caustic-Side Solvent Extraction with Optimized Solvent in the 2-cm Centrifugal Contactor Apparatus Using Dissolved Salt Cake from Tank 37H

    Energy Technology Data Exchange (ETDEWEB)

    Norato, M.A.


    A solvent extraction process for removal of cesium from alkaline solutions has been developed utilizing a novel solvent invented at the Oak Ridge National Laboratory (ORNL). This solvent consists of a calix[4]arene-crown-6 extractant (BOBCalix) dissolved in an inert hydrocarbon matrix (Isopar(R) L). An alkylphenoxy alcohol modifier added to the solvent enhances the extraction power of the calixarene and prevents the formation of a third phase. An additional additive, trioctylamine (TOA), improves stripping performance and mitigates the effects of any surfactants present in the feed stream. The solvent extraction process was successfully demonstrated with actual SRS HLW supernate during testing performed at SRTC in FY-2001. However, the solvent system has recently been optimized to enhance extractant solubility in the diluent and increase suppressor concentration. The results of the optimized solvent performance in tests using the same SRS composite waste supernate as was used FY-20 01 are described in another report.

  7. Homodiselenacalix[4]arenes: Molecules with Unique Channelled Crystal Structures. (United States)

    Thomas, Joice; Dobrzańska, Liliana; Van Meervelt, Luc; Quevedo, Mario Alfredo; Woźniak, Krzysztof; Stachowicz, Marcin; Smet, Mario; Maes, Wouter; Dehaen, Wim


    A synthetic route towards homodiselenacalix[4]arene macrocycles is presented, based on the dynamic covalent chemistry of diselenides. The calixarene inner rim is decorated with either alkoxy or tert-butyl ester groups. Single-crystal X-ray analysis of two THF solvates with methoxy and ethoxy substituents reveals the high similarity of their molecular structures and alterations on the supramolecular level. In both crystal structures, solvent channels are present and differ in both shape and capacity. Furthermore, the methoxy-substituted macrocycle undergoes a single-crystal-to-single-crystal transformation during which the molecular structure changes its conformation from 1,3-alternate (loaded with THF/water) to 1,2-alternate (apohost form). Molecular modelling techniques were applied to explore the conformational and energetic behaviour of the macrocycles.

  8. Interaction of Sulfonated Calix [n] arenes with Rhodamine B and Its Application to Determine Acetylcholine in a Real Neutral Aqueous Medium

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yong-Jun; XU,Jian; 等


    Complexation between Rhodamine B(RB) and sulfonated calix [n] arenes (SCnA) were studied by means of UV-vis spectroscopy and fluorescence spectroscopy.In the presence of sulfonated calix [n] arenes,the absorption hand of Rhodamine B shifts to longer wavelength and its intensity decreases.The formation of a host-guest type complex also results in the fluorescence quenching of Rhodamine B.The accociation constants for the RB/SCn A complexes increase in the order of SC4Acalixarenes.The fluorescence is selectively regenerated by adding acetylcholine.Based on this observation,a method to determine acetylcholine in real neutral aqueous medium was developed.

  9. Thermo gravimetric analysis of supramolecular complexes of p-tert-butylcalix[6]arene and ammonium cations: crystal structure of diethylammonium complex

    Energy Technology Data Exchange (ETDEWEB)

    Lazzarotto, Marcio [Departamento de Quimica Organica, UFRGS, Av. Bento Goncalves 9500, CEP 91501 970, C.P. 15003, Porto Alegre, Rio Grande do Sul (Brazil)]. E-mail:; Nachtigall, Francine Furtado [Departamento de Quimica Organica, UFRGS, Av. Bento Goncalves 9500, CEP 91501 970, C.P. 15003, Porto Alegre, Rio Grande do Sul (Brazil); Schnitzler, Egon [Departamento de Quimica, Universidade Estadual de Ponta Grossa, Campus de Uvaranas, Av. General Carlos Cavalcanti 4748, CEP 84030 900 Ponta Grossa, Parana, Brazil. (Brazil); Castellano, Eduardo Ernesto [Departamento de Fisica, Universidade de Sao Paulo, Sao Carlos, Av. Trabalhador Saocarlense 400, Centro, CEP 13566-590, Sao Carlos, SP (Brazil)


    Thermo gravimetric analysis of ammonium-p-tert-butylcalix[6]arene salts were carried out to determine the stoichiometry of the inclusion compounds and the temperature of leaving of the ammonium cation, as amine, from the solid phase by a reverse proton transfer reaction to calixarene. The chain length of the amine molecules and their relative basicity order are the main factors which determine the decomplexation temperatures for the ammonium salts of piperidinium, diethylammonium, ethylenediammonium, morpholinium, s-butylammonium, butylammonium, hexylammonium and triethylammonium salts of p-tert-butylcalix[6]arene anion. The solid state structure of bis-diethylammonium-p-tert-butylcalix[6]arene dianion is reported. The calix moiety adopts a 1,2,3 alternate conformation, with one ammonium as exo-calix and other as endo-calix, with an intricate array of hydrogen bonds between phenol, phenolate and ammonium cations.

  10. An Efficient Way for the Recognition of Zinc Ion via the Fluorescence Enhancement

    Institute of Scientific and Technical Information of China (English)

    桑秋光; 杨镜奎


    This study concentrates on the spectral and complexing properties of a tetraoxycalix[2]arene[2]triazine derivative bearing two bipyridines (Calix-BIPY2) in a mixture of acetonitrile : chloroform (4 : 1, V: V). The results show that Calix-BIPY2 has a highly selectivity and sensitivity towards Zn2+ over various competing eations (K+, Cu2+, Cd2+, Co2+, Fe2+, Hg2+, Ag+, Al3+ and pb2+). The complexation of Zn2+ induces a remarkable fluorescence enhancement due to combination effects of the binding strength, electron spins state of metal ions, photoinduced charge transfer (PCT) and the rigidity of the complexing unit offered by calixarene-based hosts.

  11. Selective Electrochemical Recognition of o-Phenylenediol by a Novel Calix[4]arene Derivative

    Institute of Scientific and Technical Information of China (English)

    L(U), Jian-Quan; ZHANG, Hai-Li; LU, Ping


    A new type of calixarene-modified electrode has been prepared by directly coating the surface of a glassy carbon electrode with tetrahydrofuran solution containing 25,26,27,28-tetra-(3-amidino thiopropoxy)-5,11,17,23-tetratert-butylcalix[4]arene, and applied to the investigation of electrochemical behavior of phenylenediols. The results showed that the modified electrode could selectively recognize o-phenylenediol, making the over-potential of o-phenylenediol dropped and peak current increased greatly. The anodic peak current is proportional to the concentration of o-phenylenediol in the range of 1.0 × 10-5-1.0 × 10-4 mol· L-1 with the detection limit (S/N= 3) of 1.0 ×10-7 mol·L-1. The recognizing mechanism, including electrochemical process and binging sites, was also discussed using voltammetry.

  12. Cyclodextrin-based microsensors for volatile organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Swanson, B.; Johnson, S.; Shi, J.; Yang, Xiaoguang


    Host-guest chemistry and self-assembly techniques are being explored to develop species selective thin-films for real-time sensing of volatile organic compounds (VOCs). Cyclodextrin (CD) and calixarene (CA) molecules are known to form guest-host inclusion complexes with a variety of organic molecules. Through the control of the cavity size and chemical functionality on the rims of these bucket-like molecules, the binding affinities for formation of inclusion complexes can be controlled and optimized for specific agents. Self-assembly techniques are used to covalently bond these reagent molecules to the surface of acoustic transducers to create dense, highly oriented, and stable thin films. Self-assembly techniques have also been used to fabricate multilayer thin film containing molecular recognition reagents through alternating adsorption of charged species in aqueous solutions. Self-assembly of polymeric molecules of the SAW device was also explored for fabricating species selective interfaces.

  13. Microheterogeneous Catalysis

    Directory of Open Access Journals (Sweden)

    María Marchena


    Full Text Available The catalytic effect of micelles, polymers (such as DNA, polypeptides and nanoparticles, saturable receptors (cyclodextrins and calixarenes and more complex systems (mixing some of the above mentioned catalysts have been reviewed. In these microheterogeneous systems the observed changes in the rate constants have been rationalized using the Pseudophase Model. This model produces equations that can be derived from the Brönsted equation, which is the basis for a more general formulation of catalytic effects, including electrocatalysis. When, in the catalyzed reaction one of the reactants is in the excited state, the applicability (at least formally of the Pseudophase Model occurs only in two limiting situations: the lifetime of the fluorophore and the distributions of the quencher and the probe are the main properties that define the different situations.

  14. Nanoencapsulation of Fullerenes in Organic Structures with Nonpolar Cavities (United States)

    Murthy, C. N.


    The formation of supramolecular structures, assemblies, and arrays held together by weak intermolecular interactions and non-covalent binding mimicking natural processes has been used in applications being anticipated in nanotechnology, biotechnology and the emerging field of nanomedicine. Encapsulation of C60 fullerene by cyclic molecules like cyclodextrins and calixarenes has potential for a number of applications. Similarly, biomolecules like lysozyme also have been shown to encapsulate C60 fullerene. This poster article reports the recent trends and the results obtained in the nanoencapsulation of fullerenes by biomolecules containing nonpolar cavities. Lysozyme was chosen as the model biomolecule and it was observed that there is no covalent bond formed between the bimolecule and the C60 fullerene. This was confirmed from fluorescence energy transfer studies. UV Vis studies further supported this observation that it is possible to selectively remove the C60 fullerene from the nonpolar cavity. This behavior has potential in biomedical applications

  15. Nanoencapsulation of Fullerenes in Organic Structures with Nonpolar Cavities

    Energy Technology Data Exchange (ETDEWEB)

    Murthy, C. N. [M.S. University of Baroda, Applied Chemistry Department, Faculty of Technology and Engineering (India)


    The formation of supramolecular structures, assemblies, and arrays held together by weak intermolecular interactions and non-covalent binding mimicking natural processes has been used in applications being anticipated in nanotechnology, biotechnology and the emerging field of nanomedicine. Encapsulation of C{sub 60} fullerene by cyclic molecules like cyclodextrins and calixarenes has potential for a number of applications. Similarly, biomolecules like lysozyme also have been shown to encapsulate C{sub 60} fullerene. This poster article reports the recent trends and the results obtained in the nanoencapsulation of fullerenes by biomolecules containing nonpolar cavities. Lysozyme was chosen as the model biomolecule and it was observed that there is no covalent bond formed between the bimolecule and the C{sub 60} fullerene. This was confirmed from fluorescence energy transfer studies. UV-Vis studies further supported this observation that it is possible to selectively remove the C{sub 60} fullerene from the nonpolar cavity. This behavior has potential in biomedical applications

  16. Characteristics of a novel calix[8]arene modified with carbon nanotubes thin films for metal cations detection (United States)

    Supian, Faridah Lisa; Bakar, Suriani Abu; Azahari, Noor Azyyati; Richardson, Tim H.


    This study focuses on the properties of a novel calix[8]arene that have been modified with carbon nanotubes (CNT) as ion sensor application. Calix[8]arene modified with carbon nanotubes were done by mixing CNT (Calix8A-CNT) with a novel calix[8]arene in a long ultrasonication process. This study is interesting due to the process on the attaching of the functionalization of the calixarene on the carbon nanotubes outer wall. Morphological and spectroscopic studies of Calix8A-CNT were done using Π-A isotherm, Surface Potential Probe (S-Pot), Field mission scanning electron microscopy (FE-SEM) and Raman spectroscopy in order to understand the behavior in the molecular level. This water-soluble supramolecular hybrid materials have potential as metal cations detection and nanoelectronics applications, yet the CNT provide the thermal stability to the polymers.

  17. Highly selective fluorescent chemosensor for Na+ based on pyrene-modified calix[4]arene derivative

    Institute of Scientific and Technical Information of China (English)

    WANG KeRang; GUO DongSheng; JIANG BangPing; LIU Yu


    A novel calix[4]arene derivative with pyrene fluorophores at the upper rim and tetraester ionophores at the lower rim was synthesized in six steps, and its structure was proved by NMR and ESi-MS spectro-scopies. Furthermore, the chemosensing behavior of the host compound for alkali and alkaline earth metal ions was investigated by fluorescence spectroscopy. The obtained results show that the calix-arene host can selectively bind sodium ion with the complexation stability constant of 2190 mol-1.L. The complexation with sodium ion can pronouncedly induce the excimer emission to decrease and the monomer emission to increase, whereas the addition of the other alkali and alkaline earth metal ions does not cause appreciable changes in the fluorescence spectrum of the host compound. The present calix[4]arene derivative displays potential application as fluorescent chemosensor for sodium ion.

  18. Interaction of Sulfonated Calix[n]arenes with Rhodamine B and Its Application to Determine Acetylcholine in a Real Neutral Aqueous Medium

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yong-Jun(张拥军); CAO,Wei-Xiao(曹维孝); XU,Jian(徐坚)


    Complexation between Rhodamine B (RB) and sulfonated calix [n]arenes (SCnA) were studied by means of UV-vis spectroscopy and fluorescence spectroscopy. In the presence of sulfonated calix[n ]arones, the absorption band of Rhodamine B shifts to longer wavelength and its intensity decreases. The formation of a host-guest type complex also results in the fluorescence quenching of Rhodamine B. The association constants for the RB/SCnA complexes increase in the order of SC4A <SC6A < SC8A and show dependence on the size of the cavities of the calixarenes. The fluorescence is selectively regenerated by adding acetylcholine. Based on this observation, a method to determine acetylcholine in a real neutral aqueous medium was developed.

  19. Guest exchange in dimeric capsules formed by tetra-urea calix[4]arenes. (United States)

    Vatsouro, Ivan; Alt, Ellen; Vysotsky, Myroslav; Böhmer, Volker


    Ten tetra-urea calix[4]arene derivatives with different ether residues (methyl, pentyl, benzyl, all combinations of methyl and pentyl, 1,3-dibenzyl-2,4-dipentyl), including also the tetrahydroxy compound and the 1,3-dipentyl ether, were synthesised. Their urea groups were substituted with a lipophilic residue to ensure sufficient solubility in cyclohexane. Thus, kinetics for the exchange of the included guest (benzene) against the solvent (cyclohexane) could be followed by 1H NMR spectroscopy. The apparent first order rate constants decrease with increasing size of the ether residues from methyl to benzyl by more than three orders of magnitude. This can be understood by a decreasing flexibility/mobility of the calixarene skeleton. In line with this explanation is the rather slow exchange for the tetrahydroxy compound, where the cone conformation is stabilised by a cyclic array of intramolecular OH...OH hydrogen bonds.

  20. Characterization of a sensitive and selective copper optode based on β-ketoimine modified calix[4]arene derivative

    Energy Technology Data Exchange (ETDEWEB)

    Rouis, A., E-mail: [Laboratoire des Interfaces et Matériaux Avancés (LIMA), Faculté des sciences de Monastir, Avenue de l' Environnement, 5000 Monastir (Tunisia); Echabaane, M.; Sakly, N. [Laboratoire des Interfaces et Matériaux Avancés (LIMA), Faculté des sciences de Monastir, Avenue de l' Environnement, 5000 Monastir (Tunisia); Bonnamour, I. [Institut de Chimie and Biochimie Moléculaires and Supramoléculaires (ICBMS), UMR CNRS 5246, 43 Boulevard du 11 Novembre 1918, Université Claude Bernard Lyon 1, 69100 Villeurbanne (France); Ben Ouada, H. [Laboratoire des Interfaces et Matériaux Avancés (LIMA), Faculté des sciences de Monastir, Avenue de l' Environnement, 5000 Monastir (Tunisia)


    In this paper, an optical sensor was proposed for sensitive determination of copper (II) ions in aqueous solution. The sensing membrane was prepared by coating β-ketoimine calix[4]arene derivative as ionophore on a glass plate surface. Thin β-ketoimine calix[4]arene layer was characterized by contact angle measurements showing a good surface coverage. Besides, a smooth and homogeneous morphology of the calixarene membrane was examined by atomic force microscopy (AFM). The response of the optode is based on the decrease in the absorbance signal at 309 nm upon exposure to buffer solutions containing Cu{sup 2+} ions. At a pH 6.8, the proposed sensor displays a calibration response for copper over a wide concentration range of 1.0 × 10{sup −7} M to 1.0 × 10{sup −4} M with a detection limit of 2.0 × 10{sup −8} M and response time of 7–10 min. This optode exhibits good selectivity toward copper ions in comparison with common ions including Hg{sup 2+} and Ag{sup +} ions. The copper sensing film can be regenerated using 0.01 M HNO{sub 3} solution. In addition to its high stability, repeatability and reproducibility, the sensor shows operational life time of 4 weeks. - Highlights: • Optical sensor for Cu{sup 2+} ion based on β-ketoimine calix[4]arene was developed. • Sensing mechanism involved the formation of a complex between calixarene and Cu{sup 2+}. • Satisfactory analytical sensing characteristics for determining Cu{sup 2+} were obtained.

  1. Binding properties of oxacalix[4]arenes derivatives toward metal cations; Interactions entre cations metalliques et derives des oxacalix[4]arenes

    Energy Technology Data Exchange (ETDEWEB)

    Mellah, B


    The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) {sup 1}H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na{sup +}, K{sup +}, Ca{sup 2+}, Pb{sup 2+} and Mn{sup 2+} of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li{sup +}, Ba{sup 2+}, Zn{sup 2+} and Hg{sup 2+}. A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs{sup +}, Ba{sup 2+}, Cu{sup 2+} and Hg{sup 2+} were noted. (author)

  2. Molecular engineering and fluorescence for the detection of toxic cations; Ingenierie moleculaire et fluorescence pour la reconnaissance de cations toxiques

    Energy Technology Data Exchange (ETDEWEB)

    Souchon, V


    This work is a part of the 'Toxicologie Nucleaire Environnementale' program which aims at studying the effects on the living of heavy metals or radionuclides involved in nuclear industry. Most particularly, it deals with the design of new fluorescent sensors for the selective detection of Pb{sup 2+}, Cd{sup 2+} and Cs{sup +} in biological media. Several fluorescent calixarenes possessing nitrogen atoms were synthesized and their properties as potential lead sensors were investigated. One of them could be used in experimental conditions close to biological media and new target compounds with amide functional groups were proposed. Many approaches were considered for the design of selective fluorescent sensors for cadmium. On the basis of literature results, many chelating compounds incorporating sulfur atoms were synthesized but showed no significant affinity towards cadmium. On the opposite, compounds functionalized with several pyridine-2'-yl-1,2,3-triazol fluorescent moieties linked to a {beta}-cyclodextrin or a calix[4]arene showed good affinity for cadmium in methanol, but the selectivity was found to be insufficient. In contrast, very satisfying results in terms of both selectivity and sensitivity could be obtained with the commercial calcium sensor Rhod-5N in an aqueous medium at neutral pH. Lastly, micromolar detection limits for the selective detection of caesium were reached in an aqueous medium at neutral pH thanks to a new sulfonated fluorescent calixarene with two appended crown-ethers. An original complexation mechanism was proposed and validated by molecular modelling (DFT). (author)

  3. Stabilization of coordinatively unsaturated Ir4 clusters with bulky ligands: a comparative study of chemical and mechanical effects. (United States)

    Okrut, Alexander; Gazit, Oz; de Silva, Namal; Nichiporuk, Rita; Solovyov, Andrew; Katz, Alexander


    The synthesis and characterization of new cluster compounds represented by the series Ir(4)(CO)(12-x)L(x) (L = tert-butyl-calix[4]-arene(OPr)(3)(OCH(2)PPh(2)); x = 2 and 3) is reported using ESI mass spectrometry, NMR spectroscopy, IR spectroscopy and single-crystal X-ray diffraction. Thermally driven decarbonylation of the cluster compound series represented by x = 1-3 according to the formula above is followed via FTIR and NMR spectroscopies, and dynamic light scattering in toluene solution. The propensity of these clusters to decarbonylate in solution is shown to be directly correlated with number density of adsorbed calixarene phosphine ligands and controlled via Pauli repulsion between metal d and CO 5σ orbitals. The tendency for cluster aggregation unintuitively follows a trend that is exactly opposite to the cluster's propensity to decarbonylate. No cluster aggregation is observed for clusters consisting of x = 3, even after extensive decarbonylation via loss of all bridging CO ligands and coordinative unsaturation. Some of the CO lost during thermal treatment via decarbonylation can be rebound to the coordinatively unsaturated cluster consisting of x = 3. In contrast, the clusters consisting of x = 1 and x = 2 both aggregate into large nanoparticles when treated under identical conditions. Clusters in which the calixarene phosphine ligand is replaced with a sterically less demanding PPh(2)Me ligand 6 lead to significantly less coordinative unsaturation upon thermal treatment. Altogether, these data support a mechanical model of accessibility in coordinatively unsaturated metal clusters in solution, which hinges on having at least three sterically bulky organic ligands per Ir(4) core.

  4. Calix[6]tren and copper(II): a third generation of funnel complexes on the way to redox calix-zymes. (United States)

    Izzet, Guillaume; Douziech, Bénédicte; Prangé, Thierry; Tomas, Alain; Jabin, Ivan; Le Mest, Yves; Reinaud, Olivia


    Mono-copper enzymes play an important role in biology and their functionality is based on Cu(II)/Cu(I) redox processes. Modeling a mono-nuclear site remains a challenge for a better understanding of its intrinsic reactivity. The first member of a third generation of calixarene-based mono-copper "funnel" complexes is described. The ligand is a calix[6]arene capped by a tren unit, hence presenting a N(4) coordination site confined in a cavity. Its Cu(II) complexes were characterized by electronic and EPR spectroscopies. The x-ray structure of one of them shows a five-coordinated metal ion in a slightly distorted trigonal bipyramidal geometry thanks to its coordination to a guest ligand L (ethanol). The latter sits in the heart of the hydrophobic calixarene cone that mimics the active site chamber and the hydrophobic access channel of enzymes. Competitive binding experiments showed a preference order dimethylformamide > ethanol > MeCN for L binding at the single exchangeable metal site. Cyclic voltammetry studies showed irreversible redox processes in CH(2)Cl(2) when L is an oxygen donor caused by the redox-driven ejection of the guest at the Cu(I) level. In the presence of MeCN, a pseudoreversible process was obtained, owing to a fast equilibrium between a four and a five-coordinate Cu(I) species. Finally, a redox-driven ligand interchange of dimethylformamide for MeCN at the Cu(I) state allowed the trapping of the thermodynamically less stable Cu(II)-MeCN adduct. Hence, this work represents an important step toward the elaboration of a functional supramolecular model for redox mono-copper enzymes, named redox calix-zymes.

  5. Polarizing a hydrophobic cavity for the efficient binding of organic guests: the case of calix[6]tren, a highly efficient and versatile receptor for neutral or cationic species. (United States)

    Darbost, Ulrich; Rager, Marie-Noëlle; Petit, Samuel; Jabin, Ivan; Reinaud, Olivia


    The host-guest properties of calix[6]tren 1 have been evaluated. The receptor is based on a calix[6]arene that is covalently capped at the narrow rim by a tren unit. As a result, the system presents a concave hydrophobic cavity with, at its bottom, a grid-like nitrogenous core. Despite its well-defined cavity and opening to the outside at the large rim, 1 did not behave as a good receptor for neutral molecules in chloroform. However, it exhibited efficient endo-complexation of ammonium guests. By contrast, the per-protonated host, 1.4H(+), behaved as a remarkable receptor for small organic molecules. The complexation is driven by a strong charge-dipole interaction and hydrogen bonds between the polar guest and the tetracationic cap of the calixarene. Finally, coordination of Zn(2+) to the tren core led to the asymmetrization of calixarene cavity and to the strong but selective endo-binding of neutral ligands. This study emphasizes the efficiency of a receptor presenting a concave hydrophobic cavity that is polarized at its bottom. The resulting combination of charge-dipole, hydrogen bonding, CH-pi, and van der Waals interactions highly stabilizes the supramolecular architectures. Also, importantly, the tren cap allows the tuning of the polarization, offering either a basic (1), a highly charged and acidic (1.4H(+)), or a coordination (1.Zn(2+)) site. As a result, the system proved to be highly versatile, tunable, and interconvertible in solution by simple addition of protons, bases, or metal ions.

  6. Molecular Assemblies of Porphyrins and Macrocyclic Receptors: Recent Developments in Their Synthesis and Applications

    Directory of Open Access Journals (Sweden)

    Abdirahman A. Mohamod


    Full Text Available Metalloporphyrins which form the core of many bioenzymes and natural light harvesting or electron transport systems, exhibit a variety of selective functional properties depending on the state and surroundings with which they exist in biological systems. The specificity and ease with which they function in each of their bio-functions appear to be largely governed by the nature and disposition of the protein globule around the porphyrin reaction center. Synthetic porphyrin frameworks confined within or around a pre-organized molecular entity like the protein network in natural systems have attracted considerable attraction, especially in the field of biomimetic reactions. At the same time a large number of macrocyclic oligomers such as calixarenes, resorcinarenes, spherands, cyclodextrins and crown ethers have been investigated in detail as efficient molecular receptors. These molecular receptors are synthetic host molecules with enclosed interiors, which are designed three dimensionally to ensure strong and precise molecular encapsulation/recognition. Due to their complex structures, enclosed guest molecules reside in an environment isolated from the outside and as a consequence, physical properties and chemical reactions specific to that environment in these guest species can be identified. The facile incorporation of such molecular receptors into the highly photoactive and catalytically efficient porphyrin framework allows for convenient design of useful molecular systems with unique structural and functional properties. Such systems have provided over the years attractive model systems for the study of various biological and chemical processes, and the design of new materials and molecular devices. This review focuses on the recent developments in the synthesis of porphyrin assemblies associated with cyclodextrins, calixarenes and resorcinarenes and their potential applications in the fields of molecular encapsulation/recognition, and

  7. Calix[6]tren and copper(II): A third generation of funnel complexes on the way to redox calix-zymes (United States)

    Izzet, Guillaume; Douziech, Bénédicte; Prangé, Thierry; Tomas, Alain; Jabin, Ivan; Le Mest, Yves; Reinaud, Olivia


    Mono-copper enzymes play an important role in biology and their functionality is based on Cu(II)/Cu(I) redox processes. Modeling a mono-nuclear site remains a challenge for a better understanding of its intrinsic reactivity. The first member of a third generation of calixarene-based mono-copper “funnel” complexes is described. The ligand is a calix[6]arene capped by a tren unit, hence presenting a N4 coordination site confined in a cavity. Its Cu(II) complexes were characterized by electronic and EPR spectroscopies. The x-ray structure of one of them shows a five-coordinated metal ion in a slightly distorted trigonal bipyramidal geometry thanks to its coordination to a guest ligand L (ethanol). The latter sits in the heart of the hydrophobic calixarene cone that mimics the active site chamber and the hydrophobic access channel of enzymes. Competitive binding experiments showed a preference order dimethylformamide > ethanol > MeCN for L binding at the single exchangeable metal site. Cyclic voltammetry studies showed irreversible redox processes in CH2Cl2 when L is an oxygen donor caused by the redox-driven ejection of the guest at the Cu(I) level. In the presence of MeCN, a pseudoreversible process was obtained, owing to a fast equilibrium between a fourand a five-coordinate Cu(I) species. Finally, a redox-driven ligand interchange of dimethylformamide for MeCN at the Cu(I) state allowed the trapping of the thermodynamically less stable Cu(II)-MeCN adduct. Hence, this work represents an important step toward the elaboration of a functional supramolecular model for redox mono-copper enzymes, named redox calix-zymes. PMID:15867151

  8. Quantum dot-dye hybrid systems for energy transfer applications

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Ting


    -dye complexes can also be easily transferred into water. Our approach can apply to not only dye molecules but also other organic molecules. As an example, the QDs have been complexed with calixarene molecules and the QD-calixarene complexes also have potential for QD-based energy transfer study. (orig.)

  9. Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene; Synthese et proprietes complexantes vis-a-vis de l'ion uranyle de derives carboxyliques du p-tert-butyl-calix[6]arene

    Energy Technology Data Exchange (ETDEWEB)

    Souane, R


    In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO{sub 2}{sup 2+} form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO{sub 2}) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO{sub 2}L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid ({delta}log{beta}110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO{sub 2}{sup 2+}. This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23

  10. Synthesis, Structural and Antioxidant Properties of C-p-methoxyphenylcalix[4]resorcinarene

    Directory of Open Access Journals (Sweden)

    Aishah Hasbullah


    Full Text Available The structure of Calix[4]resorcinarene is less reported compare to other calixarene derivatives because of its conformational flexibility and stability when exposed to air. The presence of solvent molecules is important for its stability in the solid state. On the other hand, the presence of several phenol groups make it a good candidate for antioxidant study. Some of them have also shown good antibacterial activity. p-methoxyphenyl calix[4]resorcinarene was synthesized and characterized by infrared and (1H , 13C NMR spectroscopic techniques. After several attempts suitable crystals were obtained and with the help of a special oil an X-ray investigation was carried out at low temperature. The calix crystallized in triclinic system with space group Pī, a= 10.6958(5, b=13.5781(7, c=16,3334(8Å, α=68.284 (4, β= 74.275(5. γ=82.589(5⁰, Z=2 and V= 2121.15(8Å3. The compound exhibits chair conformation with two resorcinol groups in anti-parallel position. The conformation is supported by eight DMSO and two DMF solvated molecules. It has a moderate antioxidant property.

  11. Characterization of an azo-calix[4]arene-based optical sensor for Europium (III) ions

    Energy Technology Data Exchange (ETDEWEB)

    Echabaane, M., E-mail: [Laboratoire d' interfaces et Materiaux Avances (LIMA) Faculte des sciences de Monastir, Avenue de l' environnement, 5000 Monastir (Tunisia); Rouis, A. [Laboratoire d' interfaces et Materiaux Avances (LIMA) Faculte des sciences de Monastir, Avenue de l' environnement, 5000 Monastir (Tunisia); Bonnamour, I. [Institut de Chimie and Biochimie Moleculaires and Supramoleculaires (ICBMS), UMR CNRS 5246, 43 Boulevard du 11 Novembre 1918, Universite Claude Bernard Lyon 1, 69100 Villeurbanne (France); Ouada, H. Ben [Laboratoire d' interfaces et Materiaux Avances (LIMA) Faculte des sciences de Monastir, Avenue de l' environnement, 5000 Monastir (Tunisia)


    Selective and sensitive optical sensor membranes (optodes) were elaborated to detect cations in aqueous solutions. The sensing films are based on chromogenic calix[4]arene derivatives. The optode membranes were studied using UV/Vis absorption spectroscopy measurements. The sensitivity of the optode has been tested for Pb{sup 2+}, Cd{sup 2+}, Mg{sup 2+} and Eu{sup 3+} ions at pH 6.8. The results showed a good selectivity response towards Eu{sup 3+}. Low selectivity coefficients were observed for Cd{sup 2+} and Mg{sup 2+} where Pb{sup 2+} can be considered as interfering ions. The characteristics of this optode such as response time, regeneration, reproducibility and lifetime are discussed. - Highlights: Black-Right-Pointing-Pointer We report optical sensing studies of chromogenic calixarene derivatives. Black-Right-Pointing-Pointer We investigate optical interaction between azo-calix[4]arene and Eu{sup 3+}. Black-Right-Pointing-Pointer We study sensitivity and selectivity of optode films. Black-Right-Pointing-Pointer We describe characteristics of optode films for determination of europium traces.

  12. Advanced electric-field scanning probe lithography on molecular resist using active cantilever (United States)

    Kaestner, Marcus; Aydogan, Cemal; Lipowicz, Hubert-Seweryn; Ivanov, Tzvetan; Lenk, Steve; Ahmad, Ahmad; Angelov, Tihomir; Reum, Alexander; Ishchuk, Valentyn; Atanasov, Ivaylo; Krivoshapkina, Yana; Hofer, Manuel; Holz, Mathias; Rangelow, Ivo W.


    The routine "on demand" fabrication of features smaller than 10 nm opens up new possibilities for the realization of many novel nanoelectronic, NEMS, optical and bio-nanotechnology-based devices. Based on the thermally actuated, piezoresistive cantilever technology we have developed a first prototype of a scanning probe lithography (SPL) platform able to image, inspect, align and pattern features down to single digit nano regime. The direct, mask-less patterning of molecular resists using active scanning probes represents a promising path circumventing the problems in today's radiation-based lithography. Here, we present examples of practical applications of the previously published electric field based, current-controlled scanning probe lithography on molecular glass resist calixarene by using the developed tabletop SPL system. We demonstrate the application of a step-and-repeat scanning probe lithography scheme including optical as well as AFM based alignment and navigation. In addition, sequential read-write cycle patterning combining positive and negative tone lithography is shown. We are presenting patterning over larger areas (80 x 80 μm) and feature the practical applicability of the lithographic processes.

  13. Calix[4]arene-linked bisporphyrin hosts for fullerenes: binding strength, solvation effects, and porphyrin-fullerene charge transfer bands. (United States)

    Hosseini, Ali; Taylor, Steven; Accorsi, Gianluca; Armaroli, Nicola; Reed, Christopher A; Boyd, Peter D W


    A calix[4]arene scaffolding has been used to construct bisporphyrin ("jaws" porphyrin) hosts for supramolecular binding of fullerene guests. Fullerene affinities were optimized by varying the nature of the covalent linkage of the porphyrins to the calixarenes. Binding constants for C60 and C70 in toluene were explored as a function of substituents at the periphery of the porphyrin, and 3,5-di-tert-butylphenyl groups gave rise to the highest fullerene affinities (26,000 M(-1) for C60). The origin of this high fullerene affinity has been traced to differential solvation effects rather than to electronic effects. Studies of binding constants as a function of solvent (toluene solubility, indicating that desolvation of the fullerene is a major factor determining the magnitude of binding constants. The energetics of fullerene binding have been determined in terms of DelatH and DeltaS and are consistent with an enthalpy-driven, solvation-dependent process. A direct relationship between supramolecular binding of a fullerene guest to a bisporphyrin host and the appearance of a broad NIR absorption band have been established. The energy of this band moves in a predictable manner as a function of the electronic structure of the porphyrin, thereby establishing its origin in porphyrin-to-fullerene charge transfer.

  14. Schiff's Bases and Crown Ethers as Supramolecular Sensing Materials in the Construction of Potentiometric Membrane Sensors. (United States)

    Faridbod, Farnoush; Ganjali, Mohammad Reza; Dinarvand, Rassoul; Norouzi, Parviz; Riahi, Siavash


    Ionophore incorporated PVC membrane sensors are well-established analyticaltools routinely used for the selective and direct measurement of a wide variety of differentions in complex biological and environmental samples. Potentiometric sensors have someoutstanding advantages including simple design and operation, wide linear dynamic range,relatively fast response and rational selectivity. The vital component of such plasticizedPVC members is the ionophore involved, defining the selectivity of the electrodes' complexformation. Molecular recognition causes the formation of many different supramolecules.Different types of supramolecules, like calixarenes, cyclodextrins and podands, have beenused as a sensing material in the construction of ion selective sensors. Schiff's bases andcrown ethers, which feature prominently in supramolecular chemistry, can be used assensing materials in the construction of potentiometric ion selective electrodes. Up to now,more than 200 potentiometric membrane sensors for cations and anions based on Schiff's bases and crown ethers have been reported. In this review cation binding and anioncomplexes will be described. Liquid membrane sensors based on Schiff's bases and crownethers will then be discussed.

  15. Cyclodextrins for drug delivery. (United States)

    Laza-Knoerr, A L; Gref, R; Couvreur, P


    Cyclodextrins (CDs) are macrocyclic oligosaccharides composed of α(1,4)-linked glucopyranose subunits. These molecules possess a cage-like supramolecular structure, comparable with the structures of crown ethers, cryptands, spherands, cyclophanes, or calixarenes. However, it took 50 years to establish the molecular structure of CDs. Owing to their capability to form inclusion complexes with a variety of guest molecules, CDs are considered as the most important supramolecular host family among all supramolecular structures mentioned above. They can form complexes with various types of molecules including inorganic, organic, or organometallic that can be radical, cationic, anionic, or neutral molecules. This phenomenon bears the name "molecular recognition," while the selectivity in the formation of complexes with enantiomeric species as guests is called "chiral recognition." In addition, the properties of the molecules forming the complexes with CDs can be modified significantly. As such, a large number of scientists have attempted to elaborate and evaluate various CD derivatives that are able to complex a variety of drugs, enhancing by this way their in vivo solubility and activity. Moreover, a large number of publications describe CD uses in other fields such as foods, textile, cosmetics, or agriculture. This review reports on the recent developments of CDs in drug delivery using various routes of administration.

  16. The Role of Galectin-1 in Cancer Progression, and Synthetic Multivalent Systems for the Study of Galectin-1. (United States)

    Cousin, Jonathan M; Cloninger, Mary J


    This review discusses the role of galectin-1 in the tumor microenvironment. First, the structure and function of galectin-1 are discussed. Galectin-1, a member of the galectin family of lectins, is a functionally dimeric galactoside-binding protein. Although galectin-1 has both intracellular and extracellular functions, the defining carbohydrate-binding role occurs extracellularly. In this review, the extracellular roles of galectin-1 in cancer processes are discussed. In particular, the importance of multivalent interactions in galectin-1 mediated cellular processes is reviewed. Multivalent interactions involving galectin-1 in cellular adhesion, mobility and invasion, tumor-induced angiogenesis, and apoptosis are presented. Although the mechanisms of action of galectin-1 in these processes are still not well understood, the overexpression of galectin-1 in cancer progression indicates that the role of galectin-1 is significant. To conclude this review, synthetic frameworks that have been used to modulate galectin-1 processes are reviewed. Small molecule oligomers of carbohydrates, carbohydrate-functionalized pseudopolyrotaxanes, cyclodextrins, calixarenes, and glycodendrimers are presented. These synthetic multivalent systems serve as important tools for studying galectin-1 mediated cancer cellular functions.

  17. A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes. (United States)

    Dorta, Reto; Shimon, Linda J W; Rozenberg, Haim; Ben-David, Yehoshoa; Milstein, David


    The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4'-dimethyl-2,2'-bipyridine in two steps and subsequently reacting it with p-tert-butylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)(2)]BF(4) or [Rh(NBD)(CH(3)CN)(2)]BF(4) (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF(4)](2) (4). Treatment of the ligand with PdCl(2)(CH(3)CN)(2) leads to the isolation of the bimetallic complex BBPC[PdCl(2)](2) (5). When the nickel precursor NiBr(2)(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr(2)](2) (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334 A (for 4) and 3.224 A (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.

  18. Cyclodextrin Derivatives as Chiral Supramolecular Receptors for Enantioselective Sensing

    Directory of Open Access Journals (Sweden)

    Uwe Pieles


    Full Text Available In view of the chiral nature of many bio-molecules (and all bio-macromolecules,most of therapeutically active compounds which target these molecules need to be chiraland “good handed” to be effective. In addition to asymmetric synthetic and separationmethodologies, enantioselective chemical sensors, able to distinguish between twoenantiomers of the same molecule, are of relevance. In order to design these sensing tools,two major classes of enantioselective layers have been developed. The first is based onmolecularly imprinted polymers which are produced (polymerized in the presence of theirtarget, thus the polymeric material keep in “memory” the size and the shape of this moleculeand the system could be used for sensing (not reviewed here. The second approach makesuse of sensitive layers containing chiral macrocyclic receptors able of stereoselectivemolecular recognition; these receptors are mainly based on cyclodextrins. In thiscontribution, are reviewed achievements in the use of native or chemically modifiedcyclodextrins for chiral sensing purposes (at interfaces. Potentialities of other chiralmacrocycles based on calixarenes, calix-resorcinarenes or crown-ethers as supramolecularreceptors for enantioselective sensing are discussed.

  19. Aqua(μ-cone-26,28-dibutoxy-25,27-bis{N-[5-(dimethylaminonaphthalene-1-sulfonyl]carbamoylmethoxy}-5,11,17,23-tetrakis(1,1-dimethylethylcalix[4]arene(2−disodium acetonitrile tetrasolvate

    Directory of Open Access Journals (Sweden)

    Pogisego Dinake


    Full Text Available The structure of the title complex, [Na2(C80H98N4O10S2(H2O]·4CH3CN, obtained after crystallization from acetonitrile, contains two formula units in the asymmetric unit (Z′ = 2 and an estimated four molecules of acetonitrile per calixarene moiety. It is unusual for two Na+ ions to occupy the lower rims of the cone calix[4]arene, as in this case, with one Na+ ion forming two O→ Na+ coordinate bonds with the two butoxy groups and four such bonds with the two N-dansyl carboxamide groups, forming six dative bonds between Na+ and O. On the other hand, the other Na+ ion forms only five O→Na+ coordinate bonds on the far end of the calix[4]arene lower rim, bringing the two dansyl groups in close proximity with each other. There also appears to be an O→Na+ coordination coming from a dangling water molecule. The structure contained both resolved and poorly resolved solvent molecules. The latter were treated using the SQUEEZE routine in PLATON [Spek (2009. Acta Cryst. D65, 148–155].

  20. Kinetic and Thermodynamic Stabilization of Metal Complexes by Introverted Coordination in a Calix[6]azacryptand. (United States)

    Inthasot, Alex; Brunetti, Emilio; Lejeune, Manuel; Menard, Nicolas; Prangé, Thierry; Fusaro, Luca; Bruylants, Gilles; Reinaud, Olivia; Luhmer, Michel; Jabin, Ivan; Colasson, Benoit


    The Huisgen thermal reaction between an organic azide and an acetylene was employed for the selective monofunctionalization of a X6 -azacryptand ligand bearing a tren coordinating unit [X6 stands for calix[6]arene and tren for tris(2-aminoethyl)amine]. Supramolecular assistance, originating from the formation of a host-guest inclusion complex between the reactants, greatly accelerates the reaction while self-inhibition affords a remarkable selectivity. The new ligand possesses a single amino-leg appended at the large rim of the calixarene core and the corresponding Zn(2+) complex was characterized both in solution and in the solid state. The coordination of Zn(2+) not only involves the tren cap but also the introverted amino-leg, which locks the metal ion in the cavity. Compared with the parent ligand deprived of the amino-leg, the affinity of the new monofunctionalized X6 tren ligand 6 for Zn(2+) is found to have a 10-fold increase in DMSO, which is a very competitive solvent, and with an enhancement of at least three orders of magnitude in CDCl3 /CD3 OD (1:1, v/v). In strong contrast with the fast binding kinetics, decoordination of Zn(2+) as well as transmetallation appeared to be very slow processes. The monofunctionalized X6 tren ligand 6 fully protects the metal ion from the external medium thanks to the combination of a cavity and a closed coordination sphere, leading to greater thermodynamic and kinetic stabilities.

  1. Development of a V-shape bis(tetraoxacalix[2]arene[2]triazine) stationary phase for high performance liquid chromatography. (United States)

    Hu, Kai; Feng, Suxiang; Wu, Mingxia; Wang, Shuang; Zhao, Wenjie; Jiang, Qiong; Yu, Ajuan; Zhang, Shusheng


    A new stationary phase for high-performance liquid chromatography was prepared by covalently bonding a V-shape cage heteroatom-bridged calixarene onto silica gel using 3-aminopropyltriethoxysilane as coupling reagent. The structure of the new material was characterized by infrared spectroscopy, elemental analysis and thermogravimetric analysis. Linear solvation energy relationship method was successfully employed to evaluate the new phase with a set of 34 solutes. The retention characteristic of the new phase shows significant similarities with ODS, as well as distinctive features. Multiple mechanisms including hydrophobic, hydrogen bonding, π-π and n-π interaction are involved. The chromatographic behavior of the phase was illustrated by using alkylbenzenes, aromatics positional isomers and flavonoids as probes. Moreover, inorganic anions were individually separated in anion-exchange mode by using the same column. Thus, multi-interaction mechanisms and mixed-mode separation of the new phase can very likely guarantee its excellent chromatographic performance for the analysis of complex samples. The column has been successfully employed for the analysis of clenbuterol in animal urine, and it is demonstrated to be suitable and a competitive alternative analytical method for the determination of clenbuterol.

  2. Antiseptic properties of two calix[4]arenes derivatives on the human coronavirus 229E. (United States)

    Geller, C; Fontanay, S; Mourer, M; Dibama, H Massimba; Regnouf-de-Vains, J-B; Finance, C; Duval, R E


    Facing the lack in specific antiviral treatment, it is necessary to develop new means of prevention. In the case of the Coronaviridae this family is now recognized as including potent human pathogens causing upper and lower respiratory tract infections as well as nosocomial ones. Within the purpose of developing new antiseptics molecules, the antiseptic virucidal activity of two calix[4]arene derivatives, the tetra-para-sulfonato-calix[4]arene (C[4]S) and the 1,3-bis(bithiazolyl)-tetra-para-sulfonato-calix[4]arene (C[4]S-BTZ) were evaluated toward the human coronavirus 229E (HCoV 229E). Comparing these results with some obtained previously with chlorhexidine and hexamidine, (i) these two calixarenes did not show any cytotoxicity contrary to chlorhexidine and hexamidine, (ii) C[4]S showed as did hexamidine, a very weak activity against HCoV 229E, and (iii) the C[4]S-BTZ showed a stronger activity than chlorhexidine, i.e. 2.7 and 1.4log₁₀ reduction in viral titer after 5min of contact with 10⁻³mol L⁻¹ solutions of C[4]S-BTZ and chlorhexidine, respectively. Thus, the C[4]S-BTZ appeared as a promising virucidal (antiseptic) molecule.

  3. Novel cinchona carbamate selectors with complementary enantioseparation characteristics for N-acylated amino acids. (United States)

    Krawinkler, Karl Heinz; Maier, Norbert M; Ungaro, Rocco; Sansone, Francesco; Casnati, Alessandro; Lindner, Wolfgang


    The synthesis and chromatographic evaluation of the enantiomer separation capabilities of covalently immobilized calix[4]arene-cinchona carbamate hybrid type receptors derived from quinine (QN) and its corresponding C9-epimer (eQN) in different solvents are reported. The receptors display complementary enantiomer separation profiles in terms of elution order, chiral substrate specificity, and mobile phase characteristics, indicating the existence of two distinct chiral recognition mechanisms. The QN-derived receptor binds the (S)-enantiomers of N-acylated amino acids more strongly, shows preferential recognition of open-chained amino acids, and superior enantioselectivity in polar media such as methanol/acetic acid. In contrast, the eQN congener preferentially recognizes the corresponding (R)-enantiomers, displays good enantioselectivity (alpha up to 1.74) for cyclic amino acids, and enhanced stereodiscriminating properties in apolar mobile phases, e.g., chloroform/acetic acid. A comparison of the enantiomer separation profiles with those of the corresponding QN and eQN tert-butyl carbamate congeners indicates no significant level of cooperativity between the calix[4]arene module and the cinchona units in terms of overall chiral recognition, most probably as a consequence of residual conformational flexibility of the calixarene module and the carbamate linkage.

  4. Calix[4]arene-Based New Neutral Sensors for Fluoride

    Institute of Scientific and Technical Information of China (English)

    LIU,Shun-Ying; MENG,Ling-Zhi; LIU,Xin; HE,Yong-Bing


    @@ The development of new receptors which can recognize neutral and charged species has attracted considerable interest in the recent past.[1] Anions such as fluoride, chloride, phosphate and carboxylate play crucial roles in a range of biological phenomena and are implicated in many disease states.[2] Investigations on molecular and/or ionic recognition by calixarenes and their derivatives as synthetic receptors have attracted increasing attention in supramolecular chemistry because of their modifiable structure.[3] However, calix[4]arenes-based neutral receptors containing thiourea and amide groups are still rare. In this paper, we report fluoride selective optical chemosensors 4 and 5, based on calix[4]arene thiourea and amide derivatives, which only show a remarkable absorption change in the presence of fluoride ions, while have no any change upon addition of other anions (Cl- Br-, I-, AcO- and H2PO4-). The association constants are 947 and 2883 mol·L-1, respectively. The synthesis of calix[4]arene derivatives 4 and 5 is outlined in the following Scheme 1.

  5. Schiff's Bases and Crown Ethers as Supramolecular Sensing Materials in the Construction of Potentiometric Membrane Sensors

    Directory of Open Access Journals (Sweden)

    Siavash Riahi


    Full Text Available Ionophore incorporated PVC membrane sensors are well-established analyticaltools routinely used for the selective and direct measurement of a wide variety of differentions in complex biological and environmental samples. Potentiometric sensors have someoutstanding advantages including simple design and operation, wide linear dynamic range,relatively fast response and rational selectivity. The vital component of such plasticizedPVC members is the ionophore involved, defining the selectivity of the electrodes' complexformation. Molecular recognition causes the formation of many different supramolecules.Different types of supramolecules, like calixarenes, cyclodextrins and podands, have beenused as a sensing material in the construction of ion selective sensors. Schiff's bases andcrown ethers, which feature prominently in supramolecular chemistry, can be used assensing materials in the construction of potentiometric ion selective electrodes. Up to now,more than 200 potentiometric membrane sensors for cations and anions based on Schiff'sbases and crown ethers have been reported. In this review cation binding and anioncomplexes will be described. Liquid membrane sensors based on Schiff's bases and crownethers will then be discussed.

  6. Evaluation of Factors Affecting Cesium Extraction Performance by Calix[4]Arene Derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Rumppe, J.L.; Delmau, L.


    Novel aza-crown derivatives of dioctyloxy-calix[4]arene crown-6 were examined for their cesium extraction performance at different pH levels. These studies are of interest in addressing high-level waste tank remediation and the removal of 137Cs, a major contributor to heat and radiation generation. Preliminary studies were done to assess the performance of these calixarene compounds under varying conditions. Results showed an increase of cesium extraction with pH as well as expected trends in diluent effects and anion selectivity. Poor extraction performance of some aza-crown derivatives raised questions regarding the possibility of intramolecular hydrogen-bonding. A novel methylated derivative was used to address these questions. Additional experiments were conducted to determine the extraction effect on pH. Results indicate an increase in cesium extraction with pH, as shown in preliminary studies. Mono-aza derivatives were shown to exhibit better cesium extraction performance than their di-aza counterparts. The methylated derivative showed poorer extraction performance than the non-methylated derivative, indicating that completely removing the possibility of intramolecular hydrogen-bonding has negative effects on extraction performance. This suggests that the hydrogen-bonding facilitates anion co-extraction, which would lead to better overall extraction. Mono-aza derivatives were shown to cause unexpected changes in pH. This could possibly be attributed to protonation of the calix crown.

  7. An approach to conductometric immunosensor based on phthalocyanine thin film. (United States)

    Sergeyeva, T A; Lavrik, N V; Rachkov, A E; Kazantseva, Z I; El'skaya, A V


    A new approach to conductometric biosensors utilizing iodine-sensitive phthalocyanine thin films has been proposed. The excellent sensitivity of the tetra-tert-butyl copper phthalocyanine (ttb-CuPc) to free iodine was used for the first time to detect a peroxidase-initiated reaction in an aqueous medium. To minimize the interfering effect of aqueous electrolytes on the impedance responses of the ttb-CuPc film itself, Au/Cr interdigitated planar electrodes bearing ttb-CuPc thin films were protected with hydrophobic gas-permeable membranes, namely thermally evaporated calixarene or plasma polymerized hexamethyldisiloxane films. Impedance spectroscopy data were analyzed in order to define the optimal operating frequency. An enzyme sensor with peroxidase immobilized in a cross-linked albumin matrix was tested. Its impedance responses were studied under variation of the substrate concentration, pH, ionic strength and buffer capacity. These results were used to define conditions for peroxidase-linked immunoassay in subsequent tests. With the developed sensor, concentrations of IgG in 0.2-2 micrograms/ml range were measured in a competitive mode with satisfactory accuracy. The detection of IgG in both test solutions and blood serum samples has been demonstrated.

  8. Colorimetric detection of Cu2+ and Pb2+ ions using calix[4]arene functionalized gold nanoparticles

    Indian Academy of Sciences (India)

    Ravi Gunupuru; Debdeep Maity; Gopala R Bhadu; Ashish Chakraborty; Divesh N Srivastava; Parimal Paul


    Calixarene functionalized gold nanoparticles (CFAuNPs) have been prepared and characterized by spectroscopic and microscopic (TEM) techniques. To use this material as potential colorimetric sensor, the binding property of this new material has been investigated with a large number of metal ions. It exhibited sharp colour change from dark brown to green and blue, detectable by naked-eye, in the presence of Cu2+ and Pb2+ ions, respectively. It has also triggered substantial change in surface plasmon resonance (SPR) band of the functionalized gold nanoparticles, which in case of Pb(II) is due to the inter particle plasmon coupling arising from the metal-induced aggregation of the nanoparticles and for Cu(II), it is because of the formation of AuCu alloy due to anti-galvanic exchange. The size and aggregation of the nanoparticles are confirmed from HRTEM images, elemental analysis and the line profiling for both the metal ions have been done by STEM-EDX analysis.

  9. Selective polymer materials: absolute determination of their sorption properties (United States)

    Jakusch, Michael; Mizaikoff, Boris


    Several types of selective materials are frequently used in chemical sensors such as natural antibodies, synthetic host substances (calixarenes, cyclodextrines, etc.) molecularly imprinted materials, or conventional polymers. For a systematic development of those materials, their sorption behavior for interesting analyte substances and potentially interfering compounds has to be thoroughly characterized, which can be a time-consuming and error-prone task. Moreover, using the respective sensor principle itself for this characterization an exact relation between the sensor signal and the underlying partition coefficient or sorption isotherm can often not be obtained. In this paper, we present an automated method for the direct determination of polymer/water partition coefficients of volatile organic compounds that consists of an automated fluid handling system, a dedicated partitioning cell and a purge-and-trap gas chromatography (PT-GC) unit. The main application of this novel system is the characterization of layer materials for infrared evanescent wave spectroscopic (IR-EWS) sensors, however an extension to other problems is conceivable. The whole experimental procedure comprising calibration of the GC system, preparation of test solutions, analyte partitioning, sample analysis, as well as the necessary cleaning steps is performed automatically under computer control. Hence, this system can be operated unattendedly, yielding a reasonable throughput with comparatively low expenditure of human labor.

  10. Selective molecular recognition by nanoscale environments in a supported iridium cluster catalyst (United States)

    Okrut, Alexander; Runnebaum, Ron C.; Ouyang, Xiaoying; Lu, Jing; Aydin, Ceren; Hwang, Son-Jong; Zhang, Shengjie; Olatunji-Ojo, Olayinka A.; Durkin, Kathleen A.; Dixon, David A.; Gates, Bruce C.; Katz, Alexander


    The active sites of enzymes are contained within nanoscale environments that exhibit exquisite levels of specificity to particular molecules. The development of such nanoscale environments on synthetic surfaces, which would be capable of discriminating between molecules that would nominally bind in a similar way to the surface, could be of use in nanosensing, selective catalysis and gas separation. However, mimicking such subtle behaviour, even crudely, with a synthetic system remains a significant challenge. Here, we show that the reactive sites on the surface of a tetrairidium cluster can be controlled by using three calixarene-phosphine ligands to create a selective nanoscale environment at the metal surface. Each ligand is 1.4 nm in length and envelopes the cluster core in a manner that discriminates between the reactivities of the basal-plane and apical iridium atoms. CO ligands are initially present on the clusters and can be selectively removed from the basal-plane sites by thermal dissociation and from the apical sites by reactive decarbonylation with the bulky reactant trimethylamine-N-oxide. Both steps lead to the creation of metal sites that can bind CO molecules, but only the reactive decarbonylation step creates vacancies that are also able to bond to ethylene, and catalyse its hydrogenation.

  11. Self-assemblies based on the "outer-surface interactions" of cucurbit[n]urils: new opportunities for supramolecular architectures and materials. (United States)

    Ni, Xin-Long; Xiao, Xin; Cong, Hang; Zhu, Qian-Jiang; Xue, Sai-Feng; Tao, Zhu


    Supramolecular architectures and materials have attracted immense attention during the last decades because they not only open the possibility of obtaining a large variety of aesthetically interesting structures but also have applications in gas storage, sensors, separation, catalysis, and so on. On the other hand, cucurbit[n]urils (Q[n]s), a relatively new class of macrocyclic hosts with a rigid hydrophobic cavity and two identical carbonyl fringed portals, have attracted much attention in supramolecular chemistry. Because of the strong charge-dipole and hydrogen bonding interactions, as well as hydrophobic and hydrophilic effect derived from the negative portals and rigid cavities of Q[n]s, nearly all research in Q[n]s has been focused on utilizing the portals and cavities to construct supramolecular assemblies similar to other macrocyclic receptors such as cyclodextrin and calixarenes. Interestingly, a recent study revealed that other weak noncovalent interactions such as hydrogen bonding and π···π stacking, as well as C-H···π and ion-dipole interactions, could also be defined as "outer-surface interactions", which are derived from the electrostatically positive outer surface of Q[n]s. These interactions could be the driving forces in the formation of various novel Q[n]-based supramolecular architectures and functional materials. In this Account, we provide a comprehensive overview of supramolecular self-assemblies based on the outer-surface interactions of Q[n]s. These outer-surface interactions include those between Q[n]s, Q[n]s and aromatic molecules, Q[n]s and calixarenes, Q[n]s and inorganic complex ions, and Q[n]s and polyoxometalates. Pioneering work has shown that such weak noncovalent interactions play very important roles in the formation of various Q[n]-based functional materials and supramolecular architectures. For example, hydrogen bonds in outer-surface interactions between Q[n] molecules not only function as the sole driving force in the

  12. 超分子化合物毛细管电色谱固定相的研究进展%Research progress in supramolecular compounds-based stationary phases for capillary electrochromatography

    Institute of Scientific and Technical Information of China (English)

    田耘; 曹小敏; 张琪; 曾昭睿


    Supramolecular chemistry is a new branch of sciences, which deals with the specific recognitions between molecules. The host-guest interactions, which exert by supramolecular compounds, can provide a promising prospect for chromatographic separations with high selec-tivities. Capillary electrochromatography (CEC) is defined as a very promising micro-separa-tion technique with high efficiency and high selectivity in recent years. As the key component of CEC, the stationary phases have been the research focus of CEC development. This paper re-views the recent progress in supramolecular compounds-based stationary phases (cyclodextrin, calixarene, crown ether and macrocyclic polyamine) for CEC since 1998.%超分子化学是一门研究分子间特定识别能力的新兴学科,超分子化合物所具有的主-客体识别能力为高选择性的色谱分离提供了广阔的发展前景.毛细管电色谱是近年来发展起来的一种高效、高选择性的微分离技术,电色谱固定相是该技术的核心部分,一直是研究的热点.本文综述了1998年以来环糊精、杯芳烃、冠醚以及大环多胺等4种超分子化合物用作毛细管电色谱固定相的研究进展情况.

  13. Enumeration of virtual libraries of combinatorial modular macrocyclic (bracelet, necklace) architectures and their linear counterparts. (United States)

    Taniguchi, Masahiko; Du, Hai; Lindsey, Jonathan S


    A wide variety of cyclic molecular architectures are built of modular subunits and can be formed combinatorially. The mathematics for enumeration of such objects is well-developed yet lacks key features of importance in chemistry, such as specifying (i) the structures of individual members among a set of isomers, (ii) the distribution (i.e., relative amounts) of products, and (iii) the effect of nonequal ratios of reacting monomers on the product distribution. Here, a software program (Cyclaplex) has been developed to determine the number, identity (including isomers), and relative amounts of linear and cyclic architectures from a given number and ratio of reacting monomers. The program includes both mathematical formulas and generative algorithms for enumeration; the latter go beyond the former to provide desired molecular-relevant information and data-mining features. The program is equipped to enumerate four types of architectures: (i) linear architectures with directionality (macroscopic equivalent = electrical extension cords), (ii) linear architectures without directionality (batons), (iii) cyclic architectures with directionality (necklaces), and (iv) cyclic architectures without directionality (bracelets). The program can be applied to cyclic peptides, cycloveratrylenes, cyclens, calixarenes, cyclodextrins, crown ethers, cucurbiturils, annulenes, expanded meso-substituted porphyrin(ogen)s, and diverse supramolecular (e.g., protein) assemblies. The size of accessible architectures encompasses up to 12 modular subunits derived from 12 reacting monomers or larger architectures (e.g. 13-17 subunits) from fewer types of monomers (e.g. 2-4). A particular application concerns understanding the possible heterogeneity of (natural or biohybrid) photosynthetic light-harvesting oligomers (cyclic, linear) formed from distinct peptide subunits.

  14. The (Calix[4]arene)chloromolybdate(IV) anion [MoCl(Calix)](-): a convenient entry into molybdenum Calix[4]arene chemistry. (United States)

    Radius, Udo; Attner, J


    The complex (HNEt(3))[MoCl(NCMe)(Calix)] (1), prepared from the reaction of [MoCl(4)(NCMe)(2)] with p-tert-butylcalix[4]arene, H(4)Calix, in the presence of triethylamine, has been used as a source of the d(2)-[Mo(NCMe)(Calix)] fragment. Complex 1 is readily oxidized with PhICl(2) to afford the molybdenum(VI) dichloro complex [MoCl(2)(Calix)] (2). Both complexes are a convenient entry point into molybdenum(VI) and molybdenum(IV) calixarene chemistry. The reaction of 1 with trimethylphosphine and pyridine in the presence of catalytic amounts [Ag(OTf)] led to the formation of neutral d(2) complexes [Mo(PMe(3))(NCMe)(Calix)] (3) and [Mo(NC(5)H(5))(NCMe)(Calix)] (4). The role of the silver salt in the reaction mixture is presumably the oxidation of the chloromolybdate anion of 1 to give a reactive molybdenum(V) species. The same reactions can also be initiated with ferrocenium cations such as [Cp(2)Fe](BF(4)). Without the presence of coordinating ligands, the dimeric complex [[Mo(NCMe)(Calix)](2)] (5) was isolated. The reaction of 1 with Ph(2)CN(2) led to the formation of a metallahydrazone complex [Mo(N(2)CPh(2))(NCMe)(Calix)] (6), in which the diphenyldiazomethane has been formally reduced by two electrons. Molybdenum(VI) complexes were also obtained from reaction of 1 with azobenzene and sodium azide in the presence of catalytic amounts of silver salt. The reaction with azobenzene led under cleavage of the nitrogen nitrogen bond to an imido complex [Mo(NPh)(NCMe)(Calix)] (7), whereas the reaction with sodium azide afforded the mononuclear molybdenum(VI) nitrido complex (HNEt(3))[MoN(Calix)] (8).

  15. Dioxygen activation at a mononuclear Cu(I) center embedded in the calix[6]arene-tren core. (United States)

    Izzet, Guillaume; Zeitouny, Joceline; Akdas-Killig, Huriye; Frapart, Yves; Ménage, Stéphane; Douziech, Bénédicte; Jabin, Ivan; Le Mest, Yves; Reinaud, Olivia


    The reaction of a cuprous center coordinated to a calix[6]arene-based aza-cryptand with dioxygen has been studied. In this system, Cu(I) is bound to a tren unit that caps the calixarene core at the level of the small rim. As a result, although protected from the reaction medium by the macrocycle, the metal center presents a labile site accessible to small guest ligands. Indeed, in the presence of O2, it reacts in a very fast and irreversible redox process, leading, ultimately, to Cu(II) species. In the coordinating solvent MeCN, a one electron exchange occurs, yielding the corresponding [CalixtrenCu-MeCN](2+) complex with concomitant release of superoxide in the reaction medium. In a noncoordinating solvent such as CH2Cl2, the dioxygen reaction leads to oxygen insertions into the ligand itself. Both reactions are proposed to proceed through the formation of a superoxide-Cu(II) intermediate that is unstable in the Calixtren environment due to second sphere effects. The transiently formed superoxide ligand either undergoes fast substitution for a guest ligand (in MeCN) or intramolecular redox evolutions toward oxygenation of Calixtren. Interestingly, the latter process was shown to occur twice on the same ligand, thus demonstrating a possible catalytic activation of O2 at a single cuprous center. Altogether, this study illustrates the oxidizing power of a [CuO2](+) adduct and substantiates a mechanism by which copper mono-oxygenases such as DbetaH and PHM activate O2 at the Cu(M) center to produce such an intermediate capable of C-H breaking before the electron input provided by the noncoupled Cu(H) center.

  16. Insights into the binding properties of a cuprous ion embedded in the tren cap of a calix[6]arene and supramolecular trapping of an intermediate. (United States)

    Izzet, Guillaume; Rager, Marie-Noëlle; Reinaud, Olivia


    Coordination of Cu(I) to a tren unit that is covalently linked to a calix[6]arene has been explored. The resulting complex revealed itself very stable in solution under an inert atmosphere, but extremely sensitive to O2 in solution as well as in the solid state. Therefore, its binding properties towards non-redox ligands have been studied in detail. The electron-rich metal center displays moderate affinity for nitrilo ligands compared to the calix[6]tris-pyridine ligand. Indeed, the binding enthalpy with acetonitrile is only -30 kJ mol(-1), whereas it is -72 kJ mol(-1) with the tris-pyridine system. In contrast, CO binding is relatively strong due to important pi-back donation from the metal center, as evidenced by the CO stretch, which was found to be less energetic (2075 cm(-1)) than that measured for ligands based on aromatic donors such as imidazole or pyridine. The conformational and dynamic properties of this calix-system have also been studied in detail. With an empty cavity or with the very small CO guest-ligand, the calix-core undergoes partial self-inclusion leading to dissymmetrical conformations. In contrast, nitrilo ligands act as "shoe-trees" that maintain the calix-core in a C(3v) symmetrical cone conformation. Very interestingly, the variable T study relative to the ligand exchange process highlighted a two-step dissociative pathway, where Cu-N bond cleavage/formation is differentiated from the nitrilo guest expulsion/inclusion from/into the calixarene cavity.

  17. A rapid stability indicating LC-method for determination of praziquantel in presence of its pharmacopoeial impurities

    Directory of Open Access Journals (Sweden)

    Hisham Hashem


    Full Text Available This study reports for the first time about a stability indicating RP-HPLC method for quantitative determination of Praziquantel (PZQ in bulk powder and dosage form and in presence of its pharmacopoeial impurities. The chromatographic separation was carried out on (Caltrex AI® calixarene column, a relatively new packing material. Chromatography was done using an isocratic binary mobile phase consisting of ACN and 25 mM ammonium acetate (NH4Ac in the ratio of 40:60 at flow rate of 1 mL min−1, 30 °C and 210 nm wavelength for detection. The elution time of PZQ was found to be 6.15 ± 0.03 min. The method was validated for system suitability, linearity, precision, limits of detection and quantitation, specificity, stability and robustness. The robustness study was done for small changes in temperature, flow rate, wavelength of detection and % of ACN in mobile phase. Stability tests were done through exposure of the analyte solution to five different stress conditions: Reflux with 1 N HCl, reflux with 1 N NaOH, reflux with 30% H2O2, thermal degradation of powder and exposure to UV radiation. Limits of detection and quantification were found to be 0.56 and 1.70 μg mL−1, respectively. The recovery value of this method was 100.30% ± 1.10 and the reproducibility was within 1.31.

  18. Calix[4]arene methylenebisphosphonic acids as inhibitors of fibrin polymerization. (United States)

    Lugovskoy, Eduard V; Gritsenko, Pavel G; Koshel, Tatyana A; Koliesnik, Ievgen O; Cherenok, Serhey O; Kalchenko, Olga I; Kalchenko, Vitaliy I; Komisarenko, Serhey V


    Calix[4]arenes bearing two or four methylenebisphosphonic acid groups at the macrocyclic upper rim have been studied with respect to their effects on fibrin polymerization. The most potent inhibitor proved to be calix[4]arene tetrakis-methylene-bis-phosphonic acid (C-192), in which case the maximum rate of fibrin polymerization in the fibrinogen + thrombin reaction decreased by 50% at concentrations of 0.52 × 10(-6) M (IC(50)). At this concentration, the molar ratio of the compound to fibrinogen was 1.7 : 1. For the case of desAABB fibrin polymerization, the IC(50) was 1.26 × 10(-6) M at a molar ratio of C-192 to fibrin monomer of 4 : 1. Dipropoxycalix[4]arene bis-methylene-bis-phosphonic acid (C-98) inhibited fibrin desAABB polymerization with an IC(50) = 1.31 × 10(-4) M. We hypothesized that C-192 blocks fibrin formation by combining with polymerization site 'A' (Aα17-19), which ordinarily initiates protofibril formation in a 'knob-hole' manner. This suggestion was confirmed by an HPLC assay, which showed a host-guest inclusion complex of C-192 with the synthetic peptide Gly-Pro-Arg-Pro, an analogue of site 'A'. Further confirmation that the inhibitor was acting at the initial step of the reaction was obtained by electron microscopy, with no evidence of protofibril formation being evident. Calixarene C-192 also doubled both the prothrombin time and the activated partial thromboplastin time in normal human blood plasma at concentrations of 7.13 × 10(-5) M and 1.10 × 10(-5) M, respectively. These experiments demonstrate that C-192 is a specific inhibitor of fibrin polymerization and blood coagulation and can be used for the design of a new class of antithrombotic agents.

  19. Caustic-Side Solvent Extraction: Chemical and Physical Properties of the Optimized Solvent

    Energy Technology Data Exchange (ETDEWEB)

    Delmau, L.H.


    This work was undertaken to optimize the solvent used in the Caustic Side Solvent Extraction (CSSX) process and to measure key chemical and physical properties related to its performance in the removal of cesium from the alkaline high-level salt waste stored in tanks at the Savannah River Site. The need to adjust the solvent composition arose from the prior discovery that the previous baseline solvent was supersaturated with respect to the calixarene extractant. The following solvent-component concentrations in Isopar{reg_sign} L diluent are recommended: 0.007 M calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) extractant, 0.75 M 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol (Cs-7SB) phase modifier, and 0.003 M tri-n-octylamine (TOA) stripping aid. Criteria for this selection included BOBCalixC6 solubility, batch cesium distribution ratios (D{sub Cs}), calculated flowsheet robustness, third-phase formation, coalescence rate (dispersion numbers), and solvent density. Although minor compromises within acceptable limits were made in flowsheet robustness and solvent density, significant benefits were gained in lower risk of third-phase formation and lower solvent cost. Data are also reported for the optimized solvent regarding the temperature dependence of D{sub Cs} in extraction, scrubbing, and stripping (ESS); ESS performance on recycle; partitioning of BOBCalixC6, Cs-7SB, and TOA to aqueous process solutions; partitioning of organic anions; distribution of metals; solvent phase separation at low temperatures; solvent stability to elevated temperatures; and solvent density and viscosity. Overall, the technical risk of the CSSX process has been reduced by resolving previously identified issues and raising no new issues.

  20. Molecular Dynamics Simulations on the solvation and interfacial behaviour of hydrophobic species. Applications to the TATB hypothesis and to the liquid/liquid extraction of cations to supercritical CO{sub 2}; Simulations par dynamique moleculaire de la solvatation et du comportement interfacial d'especes hydrophobes: application a l'hypothese TATB et a l'extraction liquide/liquide de cations par le CO{sub 2} supercritique

    Energy Technology Data Exchange (ETDEWEB)

    Schurhammer, R


    We report molecular dynamics studies on the solvation of charged hydrophobic molecules in pure liquids and at liquid / liquid interfaces. The first part of the thesis deals with the TATB hypothesis according to which the As{phi}{sub 4}{sup +} (TA{sup +}) and B{phi}{sub 4}{sup -} (TB{sup -}) ions have the same free energy of solvation in any solvent. The two ions are found to be solvated differently in pure liquids (water, chloroform, acetonitrile) as at a chloroform / water interface. These results are confirmed by free energy calculations and by simulations on iso-volume spherical S{sup +} and S{sup -} ions, which perfectly meet the TATB criteria. The many methodological tests performed show the importance of (i) the corrected treatment of 'long range interactions' (ii) the precise repartition of atomic charges (iii) the solvent models, especially for water, on the + / - charge discrimination by solvent. In the second part, in relation to the liquid / liquid extraction of cations from water to supercritical CO{sub 2}, we report the behaviour of ions (Cs{sup +}, UO{sub 2}{sup 2+}, Eu{sup 3+}), of un-complexed extractants molecules (tri-n-butylphosphate, calixarene), of their complexes with the cations and nitric acid at a preformed chloroform / water interface and during de-mixing simulations which started from a perfectly mixed CO{sub 2} / water solutions. These studies demonstrate the importance of interfacial phenomena, of simulation conditions and acid and extractant concentrations, in assisted ion extraction to supercritical CO{sub 2}. (author)

  1. Metal Vector Manipulated Molecular Self-Assembly from Werner System to Cotton System

    Institute of Scientific and Technical Information of China (English)

    YU Shu-Yan; ZHANG Zhong-Xing; HUANG Hui; LI Sheng-Hui; HUANG Hai-Ping


    A definition of metal vector was given to coordinatively unsaturated metals or asymmetrically coordinated metal complexes in which the metal center is partly blocked by inert chelating ligand(s), thus possess specific reactivity and directionality, such as cis-coordinated square Pd(Ⅱ) or Pt(Ⅱ) complexes. Metal vectors have been extensively used in coordination catalysis and molecular assembly. In 1990, Fujita [ 1 ] first demonstrated the utility of cis-coordinated square Pd(Ⅱ)or Pt(Ⅱ) complexes as a right angular 2D metal vector in the formation of molecular square, a cyclic tetramer with nano-cavity and unique molecular recognition. So far, much attention has been paid to the use of the mononuclear coordination centers (Werner-type metal vectors) in molecular assembly.As late as 1999, Cotton et al. [2] reported the use of cis-coordinated metal-metal bonded dimetal units (Cotton-type metal vectors) to direct assembly of molecular squares.This presentation includes two parts: 1) Werner-type metal vector directed molecular assembly; [3]2) Cotton-type metal vector directed molecular assembly.[4]Firstly, the Werner-type metal vector, cis-coordinated Pd(Ⅱ) nitrate, was used to direct a 6-component self-assembly. This leads to the formation of a molecular bowl or crown with syn,syn,syn conformation. These structures are analogues of calix[3]arenes and can function as anion receptors. Interestingly, an nitrate is found to distort from a trigonal plane into a trigonal pyramid when binding to the bottom of the molecular bowl.Secondly, the Cotton-type metal vector, cis-diRh(Ⅱ, Ⅱ), was used to assemble di- or poly-carboxylate anions into neutral supermolecules. Most interestingly, a calixarene-based carceplex with four cis-diRh(Ⅱ, Ⅱ) fastners was obtained[5].All self-assembling entities were studied by both X-ray crystallographic analysis and solution NMR spectra, which are consistent with the presence of assembling structures even in solution.

  2. 1,3-Diamido-calix[4]arene conjugates of amino acids: recognition of -COOH side chain present in amino acids, peptides, and proteins by experimental and computational studies. (United States)

    Acharya, Amitabha; Ramanujam, Balaji; Chinta, Jugun Prakash; Rao, Chebrolu P


    Lower rim 1,3-diamido conjugates of calix[4]arene have been synthesized and characterized, and the structures of some of these have been established by single crystal XRD. The amido-calix conjugates possessing a terminal -COOH moiety have been shown to exhibit recognition toward guest molecules possessing -COOH moiety, viz., Asp, Glu, and reduced and oxidized glutathione (GSH, GSSG), by switch-on fluorescence in aqueous acetonitrile and methanol solutions when compared to the control molecules via forming a 1:1 complex. The complex formed has been shown by mass spectrometry, and the structural features of the complexes were derived on the basis of DFT computations. The association constants observed for the recognition of Asp/Glu by Phe-calix conjugate, viz., 532/676 M(-1), are higher than that reported for the recognition of Val, Leu, Phe, His, and Trp (16-63 M(-1)) by a water-soluble calixarene (Arena, G., et al. Tetrahedron Lett. 1999, 40, 1597). For this recognition, there should be a free -COOH moiety from the guest molecule. AFM, SEM, and DLS data exhibited spherical particles with a hundred-fold reduction in the size of the complexes when compared to the particles of the precursors. These spherical particles have been computationally modeled to possess hexameric species reminiscent of the hexameric micellar structures shown for a Ag(+) complex of a calix[6]arene reported in the literature (Houmadi, S., et al. Langmuir 2007, 23, 4849). Both AFM and TEM studies demonstrated the formation of nanospheres in the case of GSH-capped Ag nanoparticles in interaction with the amido-calix conjugate that possesses terminal -COOH moiety. The AFM studies demonstrated in this paper have been very well applied to albumin proteins to differentiate the aggregational behavior and nanostructural features exhibited by the complexes of proteins from those of the uncomplexed ones. To our knowledge, this is the first report wherein a amido-calix[4]arene conjugate and its amino acid

  3. Alkali cation extraction by calix[4]crown-6 to room-temperature ionic liquids. The effect of solvent anion and humidity investigated by molecular dynamics simulations. (United States)

    Sieffert, N; Wipff, G


    We report a molecular dynamics study on the solvation of M+ (Na+ to Cs+) alkali cations and of their LM+ complexes with a calix[4]arene host (L = 1,3-dimethoxy-calix[4]arene-crown-6 in the 1,3-alternate conformation) in the [BMI][PF6] and [BMI][Tf2N] room-temperature ionic liquids "ILs" based on the BMI+ (1-butyl-3-methylimidazolium) cation. The comparison of the two liquids and the dry versus humid form of the former one (with a 1:1 ratio of H2O and BMI+PF6- species) reveals the importance of humidity: in [BMI][PF6]-dry as in the [BMI][Tf2N] liquid, the first solvation shell of the "naked" M+ ions is composed of solvent anions only (four PF6- anions, and from four to five Tf2N- anions, respectively, quasi-neutralized by a surrounding cage of BMI+ cations), while in the [BMI][PF6]-humid IL, it comprises from one to three solvent anions and about four H2O molecules. In the LM+ complexes, the cation is shielded from solvent, but still somewhat interacts with a solvent anion in the dry ILs and with water in the humid IL. We also report tests on M+ interactions with solvent anions PF6- and Tf2N- in the gas phase, showing that the AMBER results are in satisfactory agreement with QM results obtained at different levels of theory. The question of ion recognition by L is then examined by free energy perturbation studies in the three liquids, predicting a high Cs+/Na+ selectivity upon liquid extraction from an aqueous phase, in agreement with experimental results on a parent calixarene host. A similar Cs+/Na+ selectivity is predicted upon complexation in a homogeneous IL phase, mainly due to the desolvation energy of the free cations. Thus, despite their polar character, ionic liquids qualitatively behave as classical weakly polar organic liquids (e.g., choroform) as far as liquid-liquid extraction is concerned but more like polar liquids (water, alcohols) as far as complexation in a single phase is concerned.

  4. Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

    Energy Technology Data Exchange (ETDEWEB)

    Arslan, Ilke [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Gates, Bruce C. [Univ. of California, Davis, CA (United States); Katz, Alexander [Univ. of California, Berkeley, CA (United States)


    To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-the art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify

  5. Benzocyclotrimers: from the Mills-Nixon effect to gas hosting. (United States)

    Fabris, Fabrizio; Zonta, Cristiano; Borsato, Giuseppe; De Lucchi, Ottorino


    variety of synthetic approaches has yielded valuable insight into the cyclotrimerization reaction. Moreover, highly symmetric compounds, such as a D(3)-symmetric trindane and C(3v)-symmetric sumanene, have been prepared as BCT derivatives. The structure of BCTs offers a versatile three-dimensional scaffold for studying molecular recognition. Like calixarenes, BCTs form complexes with a variety of guest molecules. Recent developments include the trapping of gases in a hydrogen-bonded dimer and the encapsulation of larger molecules within a covalently linked condensation derivative. Future innovations in this fertile research area will likely include highly functionalized curved aromatics, receptors, and sensors.

  6. Supported Intrinsically Porous Oligomers as Hybrid Materials for Separations, Storage, and Sensing (United States)

    Thompson, Anthony Boone

    be promising for hydrogen storage via spillover. Finally, to demonstrate other potential uses of supported intrinsically porous oligomers, a TiO2-supported calixarene material was synthesized and used as a simple molecular sensor, opening up the possibility of using these materials for sensing. Overall, the methods used here result in robust hybrid materials with narrow adsorption site distributions and therefore are of potential use in many future applications.

  7. Macrocyclic compound as ionophores in lead(Ⅱ)ion-selective electrodes with excellent response characteristics

    Institute of Scientific and Technical Information of China (English)

    HUANG MeiRong; MA XiaoLi; LI XinGui


    Macrocyclic compounds, such as crown ethers, azacrown ethers, thiacrown ethers, calixarenes and porphyrins, which act as ionophores in lead(Ⅱ) ion-selective electrodes, are systematically summarized based on the latest literatures. The molecular structure characteristics of the ionophores are general-ized. The modification regulations for the substituted ionophores are elaborated with the purpose ofimproving the response features of the lead(Ⅱ) ion-selective electrodes assembled by them. It is pointed out that the introduction of pendant moieties which contain soft base coordination centers like N, S and P atoms is in favor of adjusting the cavity size and conformation of the macrocyclic com-pounds. Furthermore, there is synergic effect between the cavity and the donor sites of the ligand and thus the selective complexation of lead ions is easily realized, resulting in significant avoidance of the interference from other metal ions. The macrocyclic ionophore having the best response characteris-tics thus far was found to be N,N'-dimethylcyanodiaza-18-crown-6 with the detection limit of 7.0×10-8 (14.5 μg/L), which is one of the uncommon ionophores that can really eliminate the interference from silver and mercury ions. The selectivity coefficients of the ionophore for lead ions over other metal ions, such as alkali, alkaline earth and transition metal ions are in the order of 10-4 or smaller, where the se-lectivity coefficient of lead(Ⅱ) over mercury(Ⅱ) ions is much lower, down to 8.9×10-4. The structure de-sign idea for high-performance ionophore is proposed according to present results. The incorporation of nitrogen atom, especially cyano group or thiocyano group or amino/imino groups, rather than thio atom alone could result in new excellent lead ionophores. The aborative design for metacyclophanes containing aromatic nitrogen atoms with the aim of creating excellent ionophores would also become a potential research trend. The lead(Ⅱ) ion


    Energy Technology Data Exchange (ETDEWEB)

    Restivo, M.; Peters, T.; Pierce, R.; Fondeur, F.; Steeper, T.; Williams, M.; Giddings, B.; Hickman, B.; Fink, S.


    A solvent extraction system for removal of cesium (Cs) from alkaline solutions was developed utilizing a novel solvent invented at the Oak Ridge National Laboratory (ORNL). This solvent consists of a calix[4]arene-crown-6 extractant dissolved in an inert hydrocarbon matrix. A Modifier is added to the solvent to enhance the extraction power of the calixarene and to prevent the formation of a third phase. An additional additive, called a suppressor, is used to improve stripping performance. The process that deploys this solvent system is known as Caustic Side Solvent Extraction (CSSX). The solvent system has been deployed at the Savannah River Site (SRS) in the Modular CSSX Unit (MCU) since 2008. Subsequent development efforts by ORNL identified an improved solvent system that can raise the expected decontamination factor (DF) in MCU from {approx}200 to more than 40,000. The improved DF is attributed to an improved distribution ratio for cesium [D(Cs)] in extraction from {approx}15 to {approx}60, an increased solubility of the calixarene in the solvent from 0.007 M to >0.050 M, and use of boric acid (H{sub 3}BO{sub 3}) stripping that also yields improved D(Cs) values. Additionally, the changes incorporated into the Next Generation CSSX Solvent (NGS) are intended to reduce solvent entrainment by virtue of more favorable physical properties. The MCU and Salt Waste Processing Facility (SWPF) facilities are actively pursuing the changeover from the current CSSX solvent to the NGS solvent. To support this integration of the NGS into the MCU and SWPF facilities, the Savannah River Remediation (SRR)/ARP/MCU Life Extension Project requested that the Savannah River National Laboratory (SRNL) perform testing of the new solvent for the removal of Cs from the liquid salt waste stream. Additionally, SRNL was tasked with characterizing both strip (20-in long, 10 micron pore size) and extraction (40-in long, 20 micron pore size) coalescers. SRNL designed a pilot-scale experimental

  9. Ion Exchange and Solvent Extraction: Supramolecular Aspects of Solvent Exchange Volume 21

    Energy Technology Data Exchange (ETDEWEB)

    Gloe, Karsten [Technischen Universität Dresden; Tasker, Peter A [ORNL; Oshima, Tatsuya [University of Miyazaki; Watarai, Hitoshi [Institute for NanoScience Design at Osaka University; Nilsson, Mikael [University of California, Irvine


    inverse micelles swollen with water molecules. Extraction systems involving long-chain cations such as alkylammonium species or long-chain anions such as sulfonates or carboxylates proved especially prone to extensive aggregate formation. The related phenomenon of third-phase formation in SX systems, long misunderstood, is now yielding to spectroscopic and scattering techniques showing extensive long-range organization. Over the last 50 years, tools for studying the structure and thermodynamics of aggregation have grown increasingly sophisticated, leading to a rich and detailed understanding of what we can now recognize as SC phenomena in SX. In the 1970s and 1980s, the rapid growth of SC elicited a paradigm shift in SX. The influence of SC principles had two major effects on the course of SX research. First, it provided a framework for understanding the supramolecular behavior that was already well appreciated in the field of SX, though earlier without the SC terminology. Second, it provided the conceptual tools to control supramolecular behavior in SX, direct it for intended functionality, and to simplify it. Extraction by designed reagents has been steadily progressing ever since, with commercial applications emerging to successfully validate this approach. With the discovery of crown ethers in the late 1960s, the advancement of extractant design has fruitfully employed the concept of inclusion. While considerable initial progress occurred with such molecules, especially because of their affinity and selectivity for alkali and alkaline earth metals, other molecular platforms such as calixarenes have proven more versatile. Multidentate receptors for partial to full inclusion of cations, anions, ion pairs, as well as neutral species, have now become commonplace for selective extraction. This volume of Ion Exchange and Solvent Extraction examines how the principles of SC are being employed both in advancing the design of new highly selective SX systems and in


    Energy Technology Data Exchange (ETDEWEB)

    Restivo, M.; Peters, T.; Pierce, R.; Fondeur, F.; Steeper, T.; Williams, M.; Giddings, B.; Hickman, B.; Fink, S.


    A solvent extraction system for removal of cesium (Cs) from alkaline solutions was developed utilizing a novel solvent invented at the Oak Ridge National Laboratory (ORNL). This solvent consists of a calix[4]arene-crown-6 extractant dissolved in an inert hydrocarbon matrix. A Modifier is added to the solvent to enhance the extraction power of the calixarene and to prevent the formation of a third phase. An additional additive, called a suppressor, is used to improve stripping performance. The process that deploys this solvent system is known as Caustic Side Solvent Extraction (CSSX). The solvent system has been deployed at the Savannah River Site (SRS) in the Modular CSSX Unit (MCU) since 2008. Subsequent development efforts by ORNL identified an improved solvent system that can raise the expected decontamination factor (DF) in MCU from {approx}200 to more than 40,000. The improved DF is attributed to an improved distribution ratio for cesium [D(Cs)] in extraction from {approx}15 to {approx}60, an increased solubility of the calixarene in the solvent from 0.007 M to >0.050 M, and use of boric acid (H{sub 3}BO{sub 3}) stripping that also yields improved D(Cs) values. Additionally, the changes incorporated into the Next Generation CSSX Solvent (NGS) are intended to reduce solvent entrainment by virtue of more favorable physical properties. The MCU and Salt Waste Processing Facility (SWPF) facilities are actively pursuing the changeover from the current CSSX solvent to the NGS solvent. To support this integration of the NGS into the MCU and SWPF facilities, the Savannah River Remediation (SRR)/ARP/MCU Life Extension Project requested that the Savannah River National Laboratory (SRNL) perform testing of the new solvent for the removal of Cs from the liquid salt waste stream. Additionally, SRNL was tasked with characterizing both strip (20-in long, 10 micron pore size) and extraction (40-in long, 20 micron pore size) coalescers. SRNL designed a pilot-scale experimental

  11. Stimuli-responsive host-guest systems based on the recognition of cryptands by organic guests. (United States)

    Zhang, Mingming; Yan, Xuzhou; Huang, Feihe; Niu, Zhenbin; Gibson, Harry W


    CONSPECTUS: As the star compounds in host-guest chemistry, the syntheses of crown ethers proclaimed the birth of supramolecular chemistry. Crown ether-based host-guest systems have attracted great attention in self-assembly processes because of their good selectivity, high efficiency, and convenient responsiveness, enabling their facile application to the "bottom-up" approach for construction of functional molecular aggregates, such as artificial molecular machines, drug delivery materials, and supramolecular polymers. Cryptands, as preorganized derivatives of crown ethers, not only possess the above-mentioned properties but also have three-dimensional spatial structures and higher association constants compared with crown ethers. More importantly, the introduction of the additional arms makes cryptand-based host-guest systems responsive to more stimuli, which is crucial for the construction of adaptive or smart materials. In the past decade, we designed and synthesized crown ether-based cryptands as a new type of host for small organic guests with the purpose of greatly increasing the stabilities of the host-guest complexes and preparing mechanically interlocked structures and large supramolecular systems more efficiently while retaining or increasing their stimuli-responsiveness. Organic molecules such as paraquat derivatives and secondary ammonium salts have been widely used in the fabrication of functional supramolecular aggregates. Many host molecules including crown ethers, cyclodextrins, calixarenes, cucurbiturils, pillararenes, and cryptands have been used in the preparation of self-assembled structures with these guest molecules, but among them cryptands exhibit the best stabilities with paraquat derivatives in organic solvents due to their preorganization and additional and optimized binding sites. They enable the construction of sophisticated molecules or supramolecules in high yields, affording a very efficient way to fabricate stimuli

  12. Chemistry%化学

    Institute of Scientific and Technical Information of China (English)


    O612 01050129 具有微孔/大孔双孔道体系沸石材料的合成=Synthesis of Silicate Materials with Micro/Macroporous Bimodal Pore Systems[刊, 中]/王亚军(复旦大学),唐颐…∥高等学校化学学报.&2000, 21(7).&1013~1015 国家自然科学基金(29873011)资助 O612 01050130 一种新型磷酸钛大单晶的溶剂热法合成与结构研究=Studies on Solvothermal Synthesis and Structure of a New Titanium Phosphate Large Single Crystal[刊, 中]/郭阳虹(吉林大学),施展…∥高等学校化学学报.&2000, 21(7).&1010~1012 国家自然科学基金(29571011)资助 O613 01050131 一种氟气源的制备及热分解=Preparation and Thermal Decomposition of a Kind of Fluorine Source[刊, 中]/刘文元(西北核技术研究所),李辉…∥应用化学.&2000, 17(3).&300~303 国家"八六三”计划资助课题 O613 01050132 铒在HBTMPTP-正庚烷/水溶液间的传质动力学=Mass Transfer of Er(Ⅲ) between HBTMPTP Dissolved in n-Heptane and HAc-NaAc[刊, 中]/乐善堂(中科院长春应用化学所),马根祥…∥高等学校化学学报.&2000, 21(6).&832~835 在(30±0.5)℃下,用层流恒界面池研究了铒在HBTMPTP-正庚烷-0.2mol/L(H,Na)Ac萃取体系中的传质动力学.测定了该体系的界面张力,考察了水相酸度、萃取剂浓度、氯离子浓度、温度和比界面对萃取速率的影响.图6参16 国家自然科学基金(29771028,29801004)资助 O613 01050133 岩石中硼的提取分离及同位素组成的测定=Extraction and Separation of Boron in Rock Samples and lts lsotopic Determination by Thermal lonization Mass Spectrometry[刊, 中]/王刚(中科院青海盐湖所),王蕴慧…∥岩矿测试.&2000, 19(3).&169~172 介绍了一种用Na2CO3+K2CO3混合熔剂对岩石样品进行分解,用硼特效树脂和阴、阳混合离子交换树脂相结合进行岩石样品中硼的纯化分离的方法.采用该方法从岩石样品中提取、分离出来的硼能满足硼同位素质谱法测定的需要,不产生硼同位素分馏,硼同位素测定精度大多优于0.05%.表3参7 国家自然科学基金(29775028)资助 O614 01050134 有机/无机纳米杂化材料负载钛催化剂及聚合研究:Ⅰ.乙烯聚合=Study of Titanium Catalysts Supported on he Organic/Inorganic Hybrid and Polymerization Thereby:Ⅰ.Polymerization of Ethylene[刊, 中]/朱宁(中科院长春应用化学所),唐涛…∥应用化学.&2000, 17(3).&233~237 以苯乙烯与马来酸酐无规共聚物为有机组分,以正硅酸乙酯为无机组分,利用sol-gel方法制得纳米杂化材料,以此为载体合成了杂化材料载体钛系催化剂.图3表3参13 国家自然科学基金(29774028)资助 O614 01050135 硫酸锌与L-α-缬氨酸固体配合物的合成与表征=Synthesis and Characterization of Zinc Sulfate Complexes with L-α-Valine[刊, 中]/张晓玉(西北大学),杨旭武…∥应用化学.&2000, 17(3).&243~247 用半微量相平衡方法研究了ZnSO4-Val-H2O体系在25℃时的溶度图及饱和溶液折光率曲线.体系中未形成新化合物.合成了配合物Zn(Val)SO4*H2O、Zn(Val)2*H2O,并进行了表征.图2表3参13 国家自然科学基金(29871023)资助 O614 01050136 微乳液法制备超细包裹型铁粉=Preparation of Ultrafine Fe Particles by Microemulsion Method[刊, 中]/张朝平(贵州大学),邓伟…∥应用化学.&2000, 17(3).&248~251 应用W/O型微乳液法制备了纳米量级包裹型超细铁粉.由XRD、SEM、TEM和IR谱测试表明:它属于表面活性剂包裹型超细微粒.图3参9 国家自然科学基金(19872021)资助 O614 01050137 以12-钨(钼)磷杂多酸为掺杂剂的导电聚N,N-二甲基苯胺的合成与导电性=Synthesis and Conductivity of Conducting Poly N,N-Dimethaniline Doped by 12-Tungsto(Molybdo) Phosphoric Acid Used as Doping Agent[刊, 中]/张贞文(湖北大学),柳士忠…∥湖北大学学报(自然科学版).&2000, 22(3).&270~273 以12-钨(钼)磷杂多酸为掺杂剂,合成了聚N,N-二甲基苯胺.并利用ICP、元素分析、循环伏安、红外光谱及室温固体电导率的测定等手段进行了表征.结果表明,掺杂的PDMAn/PM12的室温导电率约为12-13 S/cm.图3参6 国家自然科学基金(29971010)资助 O614 01050138 Co(phen)2TATP3+与DNA在旋转金盘金环电极上的相互作用研究=Electrochemical Studies on the Interactions of the Complex of Co(phen)2TATP3+ with DNA at Rotating Au-Au Electrode[刊, 中]/李红(中山大学),蒋雄…∥高等学校化学学报.&2000, 21(7).&995~998 在pH=7.2的Tris缓冲溶液中,利用旋转环盘电极法研究了金电极上Co(phen)2TATP3+与DNA的相互作用,并根据扩散控制和电化学控制下得到的各种参数,对它们作用的模式进行了讨论.图3表2参13 国家自然科学基金(29871036)资助 O614 01050139 双金属杂原子分子筛CrCoBEA的合成、波谱及催化性能研究=Studies on the Synthesis, Spectroscopy and Catalytic Properties of CrCoBEA Metallosilicate[刊, 中]/王亚军(南开大学),唐祥海…∥高等学校化学学报.&2000, 21(7).&999~1004 采用水热晶化法首次合成出BEA结构含铬、钴双金属杂原子分子筛CrCoBEA,对晶化时间、晶化温度、成胶配比等合成条件进行了优化研究,测试其物相、波谱性质和催化性能.图6表1参15 国家自然科学基金重点项目(29733070)资助 O614 01050140 Ru(bpy)2+3在MCM-48中的组装及其发光性质=The Assembly of Tris(Bipyridine)Ruthenium(Ⅱ) in MCM-48 and Photoluminescent Properties of Assembly Products[刊, 中]/房铭(吉林大学),张萍…∥高等学校化学学报.&2000, 21(7).&1016~1017 国家自然科学基金(29771013,59795006)资助 O621 01050141 2-烯丙基-1,1-偕二金属环已烷的合成研究=Synthesis of 2-Allyl-1,1-Gemdimetallic Cyclohexane[刊, 中]/宋国强(江苏石油化工学院),王钒…∥合成化学.&2000, 8(3).&216~219 在无水乙醚中1-锂代环己烯和烯丙基溴化镁于无水溴化锌作用下发生金属化克兰荪重排反应,生成2-烯丙基-1,1-偕二金属环己烷.通过对温度、溶剂量和投料顺序等重排反应主要影响因素的考察和优化,可使2-烯丙基-1,1-偕二金属环己烷的收率达到65%.图2表3 国家自然科学基金(2947043)资助 O621 01050142 沙丘芦苇特有一小分子化合物及其对叶绿体的逆境保护效应[刊, 中]/浦铜良(兰州大学),程佑发…∥科学通报.&2000, 45(12).&1308~1313 用柱层析手段从沙漠地区沙丘芦苇叶片中分离得到一种为该生态型所特有的小分子物质,其化学特征与已报道的逆境胁迫诱导累积的溶质均不同,具多氨基芳香族强极性特征.其自然丰度与月平均气温和月极端高温值为指标的生境高温程度呈显著相关性.并主要存在于光合细胞器叶绿体中.该物质对离体叶绿体在高温下电子传递链的功能具有保护作用.图5表2参15 国家自然科学基金(39870062)资助 O621 01050143 亚胺氧自由基与酚类的反应=The Reaction of Iminoxy Radical with Phenols[刊, 中]/胡家欣(南京大学),吉民…∥高等学校化学学报.&2000, 21(7).&1045~1047 研究了亚胺氧自由基与酚类的反应,一步合成了取代苯并C023唑、萘并及喹啉并C023唑类衍生物,同时探讨了反应机理.表2参8 国家自然科学基金(29375052)资助 O621 01050144 新型磺酰胺类含氮手性配体的合成、晶体结构及催化苯乙酮的不对称氢转移反应=Studies on the Synthesis of New Sulfonylamide Ligand, Crystal Structure and Asymmetric Hydrogen Transfer Reaction of Acetophenone[刊, 中]/董春娥(中科院成都有机化学所),张俊龙…∥高等学校化学学报.&2000, 21(7).&1070~1072 国家自然科学基金(29973042)资助 O624 01050145 P+7原子团簇及其特殊配位=P+7 Clusters and Their Specical Coordinations[刊, 中]/陈明旦(厦门大学),罗海彬…∥厦门大学学报(自然科学版).&2000, 39(3).&341~346 在激光产生的磷原子团簇正离子的质谱图中,P+7具有最强的谱峰.使用分子图形软件设计出24种P+7的同分异构体,并进行分子力学、PM3半经验量子化学和ADF密度泛函优化.从各异构体成键能量的比较中可得知,最稳定的P+7构型是在最稳定的P6的双键位置增加1个磷原子所生成的结构.图2表2参23 国家自然科学基金资助 O626 01050146 硫醚双酐聚酰胺酸的合成及其热稳定性=The Synthesis and Thermal Stability of Thioether Dianhydride Poly(Amic Acid)[刊, 中]/王江洪(中科院感光化学所),沈玉全∥高等学校化学学报.&2000, 21(6).&879~883 合成了硫醚二酐和4-硝基-4′-[N,N-二(2-氨乙基)氨基]偶氮苯(二胺单体)及对应的硫醚聚酰胺酸,并对其结构进行表征.目前,这些聚合物在高敏感非线性光学材料方面显示着广泛的应用前景.图3参14 国家自然科学基金(69637010)资助 O626 01050147 具有光致变色和发光性能的有机化合物的合成及其性能研究=Synthesis and Characteristics of Compounds Having Both Photochromic and Fluorescent Character[刊, 中]/庞美丽(南开大学),王永梅…∥高等学校化学学报.&2000, 21(6).&903~907 以吲哚啉螺苯并吡喃与香豆素衍生物为原料.用DCC缩合酯化法在温和条件下合成了8种新的具有光致变色和发光性能的化合物.所得化合物同时具有光致变色和发荧光的双重特性.图2参15 国家自然科学基金(29872015)资助 O626 01050148 1,2,4-三唑并[3,2-d][1,5]-苯并氧氮杂C024化合物的合成=Synthesis of 1,2,4-Triazolo[3,2-d][1,5] Benzoxazepine Compounds[刊, 中]/刘现军(复旦大学),刘毅…∥高等学校化学学报.&2000, 21(7).&1052~1055 苯并二氢吡喃-4-酮的芳腙衍生的偶氮基碳正离子与腈发生1,3-偶极环加成反应,加成产物通过[1,2]-迁移扩环重排反应,形成新颖的三环系杂环化合物1,2,4-三唑并[3,2-d][1,5]-苯并氧氮杂C024化合物.图1表3参9 国家自然科学基金(A29872007)资助 O626 01050149 四(4-N-吡啶基)卟啉衍生物的合成及表征=Synthesis and Characterization of Meso-Tetrakis(4-Pyridyl) Porphyrin Derivatives[刊, 中]/刘淑清(吉林大学),孙浩然…∥应用化学.&2000, 17(3).&260~263 利用吡啶氮烷基化合成了一系列具有空间效应的水溶性和油溶性的四(4-N-吡啶基)卟啉衍生物及其对应的金属钴卟啉.表5参8 国家自然科学基金(29733090,29803003)资助 O627 01050150 η6-苯乙烯二羰基(三苯基膦)铬配合物的合成与聚合=Synthsis and Polymerization of η6-Styrenedicarbonyl (Triphenylphos- phine) Chromium Complexes[刊, 中]/田晓慧(华东理工大学),林嘉平…∥功能高分子学报.&2000, 13(4).&419~422 国家教委留学回国人员科研启动基金资助 O627 01050151 Schiff碱单核及双核配合物拟酶催化性能的研究=Studies on the Biomimetic Catalytic Character of New Schiff Base Mono-and Di-Nuclear Complexes[刊, 中]/陈新斌(湖南大学),朱申杰…∥高等学校化学学报.&2000, 21(7).&1048~1051 国家自然科学基金(29472055)资助 O627 01050152 Cp2TiCl2/BuiMgBr/THF体系还原二芳基二硒醚=Reduction of Diphenyldiselides with Cp2TiCl2/BuiMgBr/THF[刊, 中]/许新华(南开大学),黄宪∥高等学校化学学报.&2000, 21(7).&1073~1074 国家自然科学基金(29672008)资助 O629 01050153 环肽合成方法的研究进展=Progress in the Study on Synthetic Method of Cyclopeptide[刊, 中]/唐艳春(北京大学),田桂玲…∥高等学校化学学报.&2000, 21(7).&1056~1063 介绍了纯环肽与杂环肽合成的方法、策略及其优缺点,列举了一些常用缩合试剂,探讨了反应溶液浓度、线型肽前体化合物的结构及构象等因素对环化反应的影响.参64 国家自然科学基金(29772001)资助 O63 01050154 N-异丙基丙烯酰胺/N-乙烯基吡咯烷酮水凝胶的研究=Synthesis and Characterization of Copolymer Hydrogels of Poly(N-Isopropylacrylamide-co-N-Vinyl-2-Pyrrolidone)[刊, 中]/刘郁杨(西北工业大学),范晓东…∥功能高分子学报.&2000, 13(4).&380~384 陕西省自然科学基金资助 O63 01050155 组织工程细胞支架及其细胞亲和性改进研究进展=Cells Scaffold for Tissue Engineering and Improvement of Cells Affinity between the Cells and Cells Scaffold[刊, 中]/杨健(中科院化学所),贝建中…∥功能高分子学报.&2000, 13(4).&455~460 国家"973计划” O63 01050156 新型的乙烯聚合催化剂=Novel Catalysts for Ethylene Polymerization[刊, 中]/罗祥(中山大学),伍青∥功能高分子学报.&2000, 13(4).&481~486 广东省自然科学基金资助 O631 01050157 衣康酸对聚丙烯腈原丝结构和性能的影响=Effect of Itaconic Acid on the Structure and Properties of PAN Precursor[刊, 中]/张旺玺(山东工业大学)∥高分子学报.&2000, (3).&287~291 控制单体配比,采用丙烯腈与衣康酸自由基溶液共聚,以偶氮二异丁腈为引发剂在溶剂二甲基亚砜中合成了聚丙烯腈原丝纺丝溶液,并纺制了碳纤维前驱体聚丙烯腈原丝.通过元素分析、IR、DSC、13C-NMR等手段,讨论了共聚单体衣康酸对共聚反应及聚丙烯腈原丝结构和性能的影响.图3表3参11 国家自然科学基金(59783002)资助 O631 01050158 Cr(Ⅱ)与过氧化莰烷酮酰体系引发的活性自由基聚合反应研究=Study on "Living” Radical Polymerization Initiated by Aged Chronum (Ⅱ) Acetate and Ketopinyl Peroxide[刊, 中]/李增昌(中国科学技术大学),吴承佩…∥高分子学报.&2000, (3).&330~334 合成了过氧化莰烷酮酰(KPO),用它和Cr(Ac)2组成的氧化还原体系经陈化后,引发甲基丙烯酸甲酯,甲基丙烯酸β-羟乙酯和丙烯酸进行了聚合反应.其中甲基丙烯酸甲酯具有活性聚合特征.并有效引发含羟基单体如甲基丙烯酸β羟乙酯和丙烯酸进行聚合.图2表4参10 国家自然科学基金(29774027)资助 O631 01050159 MgCl2负载(dbm)2Ti(OPh)2催化乙烯聚合=Ethylene Polymerization with MgCl2-Supported(dbm)2Ti(OPh)2[刊, 中]/阎卫东(中科院化学所),洪瀚…∥高分子学报.&2000, (3).&358~360 报道了用MgCl2负载的二苯氧基二(二苯甲酰甲烷)钛铬合物(dbm)2Ti(OPh),以甲基铝氧烷为助催化剂,常压催化乙烯聚合的结果.图1表2参8 国家自然科学基金(29734141)重点资助 O631 01050160 单分散聚苯乙烯乳胶有序膜在二氧化硅多孔材料制备中的模板作用=Template Effects of the Ordered Film Formed from Monodispersed Polystyrene Latex[刊, 中]/杨振忠(中科院化学所),齐凯…∥高分子学报.&2000, (3).&364~367 以单分散聚苯乙烯乳胶室温形成的有序膜为模板,采用快速溶胶凝胶方法,制备了聚苯乙烯/二氧化硅杂化物,高温烧蚀除去有机物得到了二氧化硅有序孔材料,并讨论了聚苯乙烯有序膜的模板作用机理.图5参15 国家自然科学基金(29774038)资助 O631 01050161 新型含环氧端基聚芳醚酮的合成及表征=Synthesis and Characterization of a Novel Epoxy-Terminated Poly(Aryl Ether Ketoe)[刊, 中]/宣英男(大连理工大学),蹇锡高…∥高分子学报.&2000, (4).&407~410 国家"九五”攻关项目 O631 01050162 超支化聚(胺-酯)的分子设计及其制备=Synthesis and Characterization of Hyperbranched Poly(Amine-Ester)[刊, 中]/陆玉(中国科学技术大学),林德…∥高分子学报.&2000, (4).&411~414 国家自然科学基金(59673026)资助 O631 01050163 聚苯基单醚喹C023啉薄膜的性能与物理老化=The Relations between Properties and Physical Aging of Polyphenylquinoxaline Film[刊, 中]/刘万军(中科院化学所),沈静姝…∥高分子学报.&2000,(4).&415~419 国家科委基础性研究重大项目 O631 01050164 端基附壁模型聚合物环形链的构象统计理论=Configurational Statistics of Model Polymer Loop Chains Attached to a Surface[刊, 中]/廖琦(四川大学),吴大诚∥高分子学报.&2000,(4).&420~425 国家自然科学基金(29774016)资助 O631 01050165 拉格朗日-欧拉方法模拟高分子复杂流体平面收缩流动=The Lagrangian-Eulerian Method:Solutions for Planar Contraction Flow[刊, 中]/李险峰(中科院化学所),袁学锋…∥高分子学报.&2000,(4).&432~437 国家自然科学基金(29634030)资助 O631 01050166 气体膜分离用过渡金属有机络合物-聚酰亚胺杂化材料的研究=Study on Transitional Metal Organic Complex-Polyimide Hybrid Material for Gas Separation Membranes[刊, 中]/史德青(石油大学),孔瑛…∥高分子学报.&2000,(4).&457~461 科技部国家重点基础研究发展规划项目 O631 01050167 原子转移自由基聚合制备聚(丙二醇-g-苯乙烯)=Synthesis of Poly(Propylene Glycol-g-Styrene) from Atom Transfer Radical Polymerization[刊, 中]/黄昌国(华东理工大学),万小龙…∥高分子学报.&2000,(4).&467~471 国家自然科学基金(29634010)资助 O631 01050168 聚苯胺嵌入氧化石墨复合物的合成及表征=Synthesis and Characterization of Polyaniline Intercalated Graphite Oxide Composite[刊, 中]/刘平桂(北京航空材料研究院),龚克成∥高分子学报.&2000,(4).&492~495 国家自然科学基金(59836230)资助 O631 01050169 乙交酯/丙交酯共聚物的体内外降解行为及生物相容性研究=Study on the Biocompatibility and Degradation Behavior of Poly(l-Lactide-co-Glycolide) in vitro and in vivo[刊, 中]/蔡晴(中科院化学所),贝建中…∥功能高分子学报.&2000, 13(3).&249~254 国家重点基础研究发展规划(973)资助 O631 01050170 动态下HTDB/TDI体系凝胶化的研究=Study on the Gelation of Hydroxy-Teminated Polybutadiene/Diisocyanate Blends under Dynamic Condition[刊, 中]/邱方正(华东理工大学),陈建定∥功能高分子学报.&2000, 13(3).&289~292 国家教育部博士点基金资助 O631 01050171 含偶氮苯生色团的聚醚的合成与热致液晶性质=Synthesis and Thermotropic Liquid Crystalline Properties of Two Polyethers Containing Azobenzene Groups[刊, 中]/梁旭霞(中山大学),张灵志…∥功能高分子学报.&2000, 13(3).&277~284 广东省自然科学基金资助 O631 01050172 CoSalphen在壳聚糖上的固定化及对DOPA的催化氧化研究=CoSalphen Immobilized onto Chitosan and Its Activate in Catalytic Oxidation of DOPA[刊, 中]/马会宣(陕西师范大学),胡道道…∥功能高分子学报.&2000, 13(3).&301~305 陕西省自然科学基金资助 O631 01050173 环氧基活化凝胶的开环反应=Ring-Opening Reaction on Epoxy-Activated Resin[刊, 中]/查娟(生物反应器工程国家重点实验室),刘坐镇…∥功能高分子学报.&2000, 13(3).&321~324 由自制的乙酸乙烯酯-甲基丙烯酸缩水甘油酯-甲基丙烯酸烯丙酯大孔共聚物与氨水反应,实现了环氧基的开环反应.考查了不同的氨水浓度、反应温度和时间对胺化转化率的影响,并测定了形成的伯胺基的pKa值为6.9.图4表1参12 国家自然科学基金(29706002)资助 O631 01050174 纳米自组装聚电解质超薄多层膜=Polyelectrolyte Ultrathin Multilayer Films by Nano-Self-Assembly Process[刊, 中]/孙启龙(华南理工大学),王朝阳∥功能高分子学报.&2000, 13(3).&332~336 国家杰出青年科学基金(29725411)与国家自然科学基金(29804003)资助 O631 01050175 十二烷基硫酸钠减慢二苯胺-4-重氮盐及重氮树脂在水溶液中热分解反应的机理=The Mechanism of Thermal Decomposition of DDS and DR in Aqueous Solution Delayed by SDS[刊, 中]/杨伯C025(北京大学),曹维孝∥高等学校化学学报.&2000, 21(6).&969~975 国家自然科学基金(59633110及29774001)资助 O631 01050176 芘标记磺酸基聚电解质在水与DMSO中的荧光光谱=Fluorescence Spectra of Pyrene Labeled Polyelectrolytes with Sulfonate Groups in Water and DMSO[刊, 中]/高峰(华南理工大学),严宇…∥高等学校化学学报.&2000, 21(6).&976~979 国家自然科学基金(29804003)与国家杰出青年科学基金(29725411)资助 O631 01050177 尼龙1012的Brill转变=Brill Transition of Nylon 1012[刊, 中]/李勇进(上海交通大学),颜德岳…∥高等学校化学学报.&2000, 21(6).&983~984 国家自然科学基金(29974017)资助 O631 01050178 热致液晶含氯侧基聚芳醚酮的单晶状条带织构=The Single Crystal-Like Banded Textures in the Films of a Thermotropic Liquid Crystalline Poly(Aryl Ether Ketone) Containing a Lateral Chloro Group[刊, 中]/富露祥(中科院长春应用化学所),张善举…∥高等学校化学学报.&2000, 21(6).&988~990 国家自然科学基金(29974032)资助 O631 01050179 具有RAFT链转移过程的活性自由基聚合的Monte Carlo模拟=Monte Carlo Simulation on Living Radical Polymerization with RAFT Process[刊, 中]/李莉(复旦大学),何军坡…∥高等学校化学学报.&2000, 21(7).&1146~1148 国家自然科学基金资助 O631 01050180 C60-苯乙烯-顺丁烯二酸酐的三元自由基共聚=Free Radical Ternary Copolymerization of C60 with Styrene and Maleic Anhydride[刊, 中]/官文超(华中理工大学),雷洪…∥高等学校化学学报.&2000, 21(7).&1149~1150 国家自然科学基金(29674010)资助 O631 01050181 聚(苯乙烯-b-2-甲基-2-C023唑啉)嵌段共聚物的合成=Studies on Synthesis of P(S-b-Me-OXZ) Block Copolymers[刊, 中]/刘燕飞(华东理工大学),万小龙…∥高等学校化学学报.&2000, 21(7).&1157~1159 国家自然科学重点基金(29634010-2)资助 O631 01050182 乙丙共聚物接枝马来酸酐反应机理的模拟研究=Investigation of Reaction Mechanism of Maleic Anhydride Grafted onto Ethylene-Propylene Copolymer[刊, 中]/黄宏亮(中科院长春应用化学所),姚占海…∥应用化学.&2000, 17(3).&256~259 国家自然科学基金(59873022)资助 O631 01050183 稀土催化丁二烯-异戊二烯共聚合过程中的原位环化反应=In situ Cyclization in the Course of Butadiene Isoprene Copolymerization with Nd-Based Catalyst[刊, 中]/董为民(中科院长春应用化学所),逄束芬…∥应用化学.&2000, 17(3).&272~275 国家自然科学基金(29574179)资助 O631 01050184 计算机模式识别在颜料表面改性中的应用=Study on the Application of Pattern Recognition with a Computer in Surface Modification of Pigment[刊, 中]/严乐美(天津大学),杨桂琴…∥天津大学学报.&2000, 33(3).&344~347 国家自然科学基金(29376254)资助 O631 01050185 共混物中聚氯乙烯凝胶化度测试=Studies on Gelling Value of Polyvingyl Chloride in the Blend[刊, 中]/何本桥(湖北大学),张玉红…∥湖北大学学报(自然科学版).&2000, 22(4).&367~370 湖北省自然科学基金资助 O631 01050186 二氧化硅模板技术制备三维有序聚苯乙烯孔材料[刊, 中]/容建华(中科院化学所),杨振忠…∥科学通报.&2000, 45(15).&1627~1630 以单分散二氧化硅颗粒形成的有序结构为模板,制备了聚苯乙烯孔材料.通过扫描电子显微镜观察了模板、复合物及有序多孔聚苯乙烯的形态.结果表明,所合成的多孔材料中,孔大小均匀,空间排布高度有序,且结构与模板中二氧化硅小球自组装方式完全相同.图6参8 国家自然科学基金(20023003)资助 O631 01050187 光导性偶氮聚合物材料的设计[刊, 中]/周雪琴(浙江大学),陈红征…∥自然科学进展.&2000, 10(6).&543~548 以电荷转移理论为指导,对偶氮聚合物材料结构进行设计,获得了两类光导性偶氮聚合物材料,并对其结构和光导性进行了分析与讨论.图4表1参16 国家自然科学基金(59333071,69890230)资助 O631 01050188 聚合物复合材料中填料的摩擦学作用=Tribological Actions of Filiers in Polymer Composites[刊, 中]/薛群基(中科院兰州化学物理所),阎逢元∥中国科学基金.&2000, 14(4).&211~215 综述了就填料对聚合物复合材料的结构和摩擦学行为的影响,并对目前研究过程中所存在的问题进行了简要分析.图3参29 国家自然科学基金资助 O633 01050189 双马来酰亚胺树脂链结构对熔点和反应活性的影响=The Effect of Chain Structure of Bismaleimide Resins on Melting Point and Reactivity of Reaction[刊, 中]/刘润山(湖北省化学研究所),赵三平…∥功能高分子学报.&2000, 13(4).&487~493 湖北省自然科学基金资助 O636 01050190 高分子固体电解质材料研究进展=Advances in Material of Solid Polymer Electrolytes[刊, 中]/赵地顺(河北科技大学),孙凤霞…∥功能高分子学报.&2000, 13(4).&469~475 河北省自然科学基金资助 O64 01050191 Ru(bpy)2(NCS)2染料敏化CdS/Zn2+-TiO2复合半导体纳米多孔膜的光电化学=Photoelectrochemistry of CdS/Zn2+-TiO2 Composite Semiconductor Nanoporous Films Sensitized by Ru-(bpy)2(NCS)2 Dye[刊, 中]/张莉(北京大学),王艳芹…∥高等学校化学学报.&2000, 21(7).&1075~1079 国家自然科学基金(29773003)资助 O641 01050192 富勒烯笼结构的平面展示法[刊, 中]/叶大年(中科院地质与地球物理所),艾德生…∥科学通报.&2000, 45(16).&1781~1785 采用船式F5和F6与海燕式F5和F6分别表示富勒烯笼几何结构的两种平面图.这些平面图最大的优点是:(1)不破坏富勒烯笼的空间对称性;(2)可以非常清楚地展示出结构中F5和F6的配位形式.这为富勒烯笼的结构几何研究打下了基础.图3参17 国家自然科学基金(49872019)资助 O641 01050193 布朗扩散系数对胶体分形粒子簇扩散控制聚集动力学影响的Monte Carlo模拟=Monte Carlo Simulation to the Effect of Cluster Brownian Diffusion Coefficient on the Colloidal Fractal Cluster Aggregation Kinetics[刊, 中]/王惠(南开大学),王贵昌…∥高等学校化学学报.&2000, 21(6).&922~925 使用表征粒子簇结构的几何形状因子,通过对扩散控制聚集过程的模拟,从微观或介观层次研究了粒子簇结构对粒子簇增长速率和速率常数的影响规律,并与实验结果进行了对比分析.图4表1参15 国家自然科学基金(29573109)资助 O641 01050194 一些富勒烯C60双加成物稳定性的理论研究=Theoretical Studies on the Stabilities of Some C60 Bis-Adducts[刊, 中]/陈中方(南开大学),王贵昌…∥高等学校化学学报.&2000, 21(7).&1127~1129 国家自然科学基金(29773022)资助 O641 01050195 M(bpy)+32(M=Fe,Ru,Os)电子结构与相关性质=Electronic Structure and Related Chemical Properties of Complexes(M=Fe,Ru,Os)[刊, 中]/郑康成(中山大学),匡代彬…∥物理化学学报.&2000, 16(7).&608~612 报道了对配合物(M=Fe,Ru,Os)的量子化学密度泛函法研究的结果,探讨的电子结构特征及相关性质,特别是中心原子对配合物的配位键长、光谱性质、电荷布居及化学稳定性等的影响规律.图2表6参14 国家自然科学基金资助 O642 01050196 纳米HZSM-5分子筛的热稳定性=Thermostability of Nanosized HZSM-5 Zeolite[刊, 英]/张维萍(中科院大连化物所),包信和∥催化学报.&2000, 21(3).&195~196 科技部攀登计划项目 O642 01050197 微量热法研究硒对大肠杆菌生长代谢的作用=Microcalorimetric Study of the Action of Seleniumcontaining Complexes on Growth Metabolism of Escherichia coli[刊, 中]/李曦(武汉大学),刘义…∥物理化学学报.&2000, 16(6).&568~572 采用微量热法测定了Na2SeO3、吗啉、硒代吗啉和N,N'-亚基双硒代吗啉对大肠杆菌作用的热功率输出曲线,根据热功率输出曲线求算在这些药物作用下,大肠杆菌生长代谢的速率常数,并对它们的作用特征进行了比较.图2表1参7 国家自然科学基金资助 O642 01050198 反相气相色谱法测定溶剂在PBMA中的无限稀释活度系数=Measurement of Infinite Diluted Activity Coefficient of Solvent in PBMA by Inverse Gas Chromatography Method[刊, 中]/冯媛媛(华东理工大学),叶汝强…∥华东理工大学学报.&2000, 26(3).&305~308 用反相气相色谱方法测定了16种溶剂在聚甲基丙烯酸丁酯(PBMA)中343~433K范围内的无限稀释活度系数,并用周浩等的高分子溶液分子热力学模型对实验结果进行了关联,结果令人满意.图8表2参15 国家自然科学基金(29976011)资助 O643 01050199 海泡石对非晶态NiB合金催化剂的改性研究=Studies on the Modification of Sepiolite for Amorphous NiB Alloy Catalyst[刊, 中]/石秋杰(南昌大学),陈昭萍…∥物理化学学报.&2000, 16(6).&501~506 以常压气相苯加氢为探针反应,考察了酸改性前后海泡石的加入对非晶态NiB合金催化剂的加氢及抗硫性能的影响,用TPR、TPD表征了催化剂的表面性质,测定了酸改性前后海泡石的比表面及孔径分布,并与活性进行了关联.图3表3参12 国家自然科学基金资助 O643 01050200 F+NCO反应的机理和动力学=Mechanism and Kinetics of the F+NCO Reaction[刊, 中]/侯华(山东大学),王宝山…∥物理化学学报.&2000, 16(6).&517~521 高等学校博士学科点专项科研基金资助 O643 01050201 激光溅射下原子团簇生长的非平衡力学(Ⅱ)=Non-Equilibrium Kinetics of Clusters Growth under Laser Ablation(Ⅱ)[刊, 中]/曹玉群(厦门大学),黄荣彬…∥物理化学学报.&2000, 16(7).&621~626 国家自然科学基金(29890210,29773040)资助 O643 01050202 双(2,4-二甲基戊二烯基)氯化钆的合成及晶体结构=Synthesis and Structure of Bis(2,4-Dimethylpentadienyl)Gadolinium Chloride[刊, 中]/王建辉(吉林大学),母瀛…∥高等学校化学学报.&2000, 21(6).&829~831 国家自然科学基金(29672013,29754143)资助 O643 01050203 温控相转移催化&&水/有机两相催化新进展=Thermoregulated Phase-Transfer Catalysis&&Recent Advances in Water/Organic Biphasic Catalysis[刊, 中]/金子林(大连理工大学),梅建庭…∥高等学校化学学报.&2000, 21(6).&941~946 综述了"温控相转移催化”的原理,温控膦配体的设计、合成及其在水溶性极小的底物高碳烯烃的水/有机两相氢甲酰化反应中的应用效果.图4表5参35 国家自然科学基金(29792074)资助 O643 01050204 Cr-HMS合成、表征及其在催化氧化反应中的应用=Synthesis, Characterization of Cr-HMS and the Application in Catalytic Oxidation[刊, 中]/乐洪咏(复旦大学),华伟明…∥高等学校化学学报.&2000, 21(7).&1101~1104 合成了一系列不同Cr含量的Cr-HMS介孔分子筛,并对其物化性质进行了表征.结果表明,Cr的引入降低了介孔分子筛骨架结构的规整度和孔径的均一程度.Cr-HMS对苯羟基化和环己烷氧化反应均表现出良好的催化活性.并且随Cr含量的增加,催化活性呈火山型分布.图3表3参14 国家自然科学基金(29873011)资助 O643 01050205 新型甲烷无氧芳构化催化剂MoO3/MCM-49=A Novel Catalyst of MoO3/MCM-49 over Nonoxidative Aromatization of CH4[刊, 中]/许宁(吉林大学),阚秋斌…∥高等学校化学学报.&2000, 21(7).&1113~1114 国家自然科学基金(29973011)资助 O643 01050206 以TiCl4为钛源合成钛硅分子筛=Synthesis of Titanosilicalite Using Titanium Tetrachloride as Titanium Source[刊, 英]/张义华(大连理工大学),王祥生∥催化学报.&2000, 21(3).&197~198 以四丙基溴化铵为模板剂,以四氯化钛为钛源,研究了合成小晶粒钛硅分子筛(TS-1)的合成路线.合成的TS-1样品在丙烯环氧化反应中显示有较高的活性(96%)和选择性(95%),H2O2利用率高于95%.图3表1参8 国家自然科学基金(29792071)资助 O643 01050207 稀土氧化物在Fe1-xO基氨合成催化剂中的作用规律=Regular Effect of Rare Earth Oxide on Fe1-xO Catalyst for Ammonia Synthesis[刊, 中]/季德春(浙江工业大学),李小年∥催化学报.&2000, 21(3).&199~203 考察了稀土氧化物对Fe1-xO基催化剂性能的影响.结果表明,稀土氧化物与Fe1-xO作用生成一种复合氧化物REFeO3,从而促进了催化剂的还原,这种促进作用随稀土离子半径不同呈现规律性变化.图1表6参14 国家自然科学基金(29706011)资助 O643 01050208 光电催化降解磺基水杨酸的研究=Study of Photoelectrocatalytic Degradation of Sulfosalicylic Acid[刊, 中]/刘鸿(中科院大连化学物理所),冷文华∥催化学报, 21(3).&209~212 建立了以TiO2/Ni为工作电极、泡沫镍为对电极、饱和甘汞电极为参比电极的光电催化反应体系,研究了在磺基水杨酸(SSal)的光电催化降解过程中,外加电压和溶液pH值对降解速率的影响.图5表1参18 国家自然科学基金(29877024)资助 O643 01050209 多孔TiO2薄膜的表面微结构对甲基橙光催化脱色的影响=Effect of Surface Microstructure of Porous TiO2 Thin Films on Photocatalytic Decolorization of Methyl Orange[刊, 中]/余家国(武汉工业大学),赵修建∥催化学报.&2000, 21(3).&213~216 湖北省自然科学基金资助 O643 01050210 γ-Mo2N催化剂上的乙炔选择加氢=Selective Hydrogenation of Ethyne on γ-Mo2N[刊, 中]/郝志显(中科院大连化学物理所),魏昭彬∥催化学报.&2000, 21(3).&217~220 对γ-Mo2N催化剂上乙炔加氢反应进行了研究.在150℃的反应温度下,乙炔转化率为95%,乙烯选择性达80%,乙烷选择性为4%,丁烯选择性为10%.反应温度和空速对产物的选择性没有明显的影响.图4参17 国家自然科学基金(29625305)资助 O643 01050211 WO3/ZrO2固体强酸催化剂上异丁烷/丁烯的烷基化反应:Ⅱ.过渡金属的助催化作用=Study on Alkylation of Isobutane with Butene over WO3/ZrO2 Strong Solid Acid:Ⅱ. Promotions Effect of Transition Metal[刊, 中]/孙闻东(中科院长春应用化学所),吴越∥催化学报.&2000, 21(3).&229~233 制备了一系列用过渡金属活化的WO3/ZrO2固体强酸催化剂,并对其晶型结构、表面状态和酸量进行了表征.图7表2参22 国家自然科学基金(29792076)资助 O212 01050212 超细镍基催化剂上CH4-CO2重整反应的性能:Ⅰ.制备方法对催化剂结构和还原性能的影响=CH4 Reforming with CO2 over Superfine Ni-Based Catalysts:Ⅰ. Effects of Preparation Methods on Structure and TPR of Catalysts[刊, 中]/许峥(清华大学),张鎏∥催化学报.&2000, 21(3).&234~238 国家博士点基金资助 O643 01050213 SO2对Co3O4/Al2O3选择性催化氧化NO的影响=Effect of SO2 on Catalytic Oxidation of NO over Co3O4/Al2O3[刊, 中]/赵秀阁(华东理工大学),肖文德∥催化学报.&2000, 21(3).&239~242 采用流动态原位IR,TPD及XPS技术研究了NO及SO2在Co3O4/Al2O3金属氧化物催化剂表面上的吸附及脱附行为,并与该催化剂上模拟烟道气中NO的选择性催化氧化活性相关联,考察了SO2对该反应过程的影响及作用机理.图5参13 国家自然科学基金(29633030)资助 O643 01050214 Lewis酸对杂多酸催化异丁烷/丁烯烷基化反应的作用=Effect of Lewis Acid on Alkylation of Isobutane with Butene[刊, 中]/赵振波(中科院长春应用化学所),吴越∥催化学报.&2000, 21(3).&243~246 考察了SbCl5对杂多酸(HPA)催化异丁烷/丁烯烷基化反应的修饰作用,用Hammett指示剂测定了SbCl5/HPA催化剂的酸强度.结果表明,经SbCl5修饰的HPA的酸强度有所提高,SbCl5的加入量、反应温度及反应时间对烷基化油收率及产物分布均有不同的影响.图5表2参15 国家自然科学基金(29792076)资助 O643 01050215 微波固相法制备的ZnCl2/Y在α-蒎烯环氧化物重排反应中的催化性能=Catalytic Performance of ZnCl2/Y Catalyst Prepared by Solid-State Microwave Irradiation for Rearrangement Reaction of α-Pinene Oxide[刊, 中]/尹笃林(湖南师范大学),银董红∥催化学报.&2000, 21(3).&251~254 国家自然科学基金(29572042,29972011)资助 O643 01050216 Co-Mo/HZSM-5甲烷无氧芳构化催化剂上的积炭=Characterization of Coke on Co-Mo/HZSM-5 Catalyst for Methane Dehydro-Aromatization in the Absence of Oxygen[刊, 中]/田丙伦(中科院大连化学物理所),徐奕德∥催化学报.&2000, 21(3).&255~258 国家重点基础研究发展规划项目 O643 01050217 热处理改性的活性炭纤维的脱硫活性=Desulfurization Activity of Activated Carbon Fiber Modified by Heat Treatment[刊, 中]/李开喜(中科院山西煤炭化学所),凌立成∥催化学报.&2000, 21(3).&264~268 考察了在O2和水蒸气存在下高温热处理对活性炭纤维(ACF)催化转化SO2为H2SO4的活性的影响,关联了ACF表面含氧官能团的种类及数量与其脱硫活性之间的关系.图4表2参20 国家自然科学基金(29633030)资助 O643 01050218 制备方法对锶改性氧化铝的高温热稳定性的影响=The Influence of Preparation Methods on the Thermal Stability of Alumina Modified by Strontium[刊, 中]/刘勇(复旦大学),陈晓银∥催化学报.&2000, 21(3).&273~275 福特-中国研究与发展基金资助 O643 01050219 NO在氧化铝负载的Pd催化剂上吸附的TPD-MS研究=TPD-MS Study of NO Adsorption on Alumina Supported Pd Catalysts[刊, 中]/刘振林(中国科技大学),伏义路∥催化学报.&2000, 21(3).&279~282 福特-中国研究与发基金资助项目 O643 01050220 不同焙烧气氛对氟化镁表面碱性的影响=The Effect of Different Calcination Atmosphere on the Surface Basicity of Magnesium Oxide[刊, 中]/孟明(中国科技大学),林培琰∥催化学报.&2000, 21(3).&286~288 在不同气氛中600℃下焙烧Mg(OH)2制得了MgO样品.结果表明,Mg(OH)2经焙烧后分解为MgO.样品的比表面积受焙烧气氛的影响,真空中制备的样品比表面积最大,而空气中制备的样品比表面积最小.真空中制备的样品具有最多的碱位和最强的碱性.图3表2参8 国家自然科学基金(29973037)资助 O643 01050221 Ni改性Cu/Mn/ZrO2催化剂上合成低碳混合醇的研究=Synthesis of Mixed Higher Alcohols by CO Hydrogenation over Ni-Modified Cu/Mn/ZrO2 Catalyst[刊, 中]/陈小平(中科院山西煤炭化学所),吴贵升∥催化学报.&2000, 21(4).&301~304 国家自然科学基金(29873064)资助 O643 01050222 超细镍基催化剂上CH4-CO2重整反应的性能:Ⅱ.制备方法对催化和抗积碳性能的影响=CH4 Reforming with CO2 over Superfine Ni-Based Catalysts:Ⅱ.Effects of Preparation Methods on Reactivity and Carbon Deposition over Catalysts[刊, 中]/许峥(清华大学),张鎏∥催化学报.&2000, 21(4).&309~313 国家博士点基金资助 O643 01050223 合成甲基叔丁基醚的分子筛催化剂研究=A Study of Zeolite Catalysts for Synthesis of Methyl tert-Butyl Ether[刊, 中]/李永红(天津大学),王莅∥催化学报.&2000, 21(4).&323~326 中国石油化工集团公司资助 O643 01050224 二苯并噻吩在CoMoNx催化剂上的加氢脱硫=Hydrodesulfurization of Dibenzothiophene over Cobalt-Promoted Molybdenum Nitride Catalysts[刊, 中]/柳云骐(石油大学),刘晨光∥催化学报.&2000, 21(4).&337~340 中国石油天然气集团公司资助 O643 01050225 锆助剂含量对钴基费-托合成催化剂的影响=Effect of ZrO2 Loadings on Catalytic Performance of Co/SiO2 for F-T Synthesis[刊, 中]/陈建刚(中科院山西煤炭化学所),相宏伟∥催化学报.&2000, 21(4).&359~362 国家重点基础研究发展规划项目 O643 01050226 一种天然气直接转化制乙烯的新过程=A Novel Process for Direct Conversion of Natural Gas to Ethylene[刊, 英]/朱爱民(中科院大连化物所),田志坚∥催化学报.&2000, 21(4).&395~396 国家科技部资助项目 O643 01050227 N,N-二甲基胺乙基膦酸-磷酸氢锆为载体的新型固体碱研究=Study on Solid Base Supported on Zirconium Dimethyl Aminoethylphosphonate-Phosphate[刊, 中]/龚成斌(中科院大连化学物理所),曾仁权…∥应用化学.&2000, 17(3).&264~267 国家自然科学基金资助 O643 01050228 丙烷在钒-磷混合氧化物催化剂上晶格氧氧化及其循环流化床工艺=Oxidation of Propane over Vanadium-Phosphorus Oxides Catalyst by Lattice Oxygen and Its Circulating Fluidized Bed Process[刊, 中]/王鉴(浙江大学),赵如松…∥应用化学.&2000, 17(3).&313~315 用脉冲色谱研究了丙烷在钒-磷混合氧化物催化剂上的选择氧化反应,并结合TPD和XRD表征结果,证明丙烷是与催化剂的晶格氧反应生成丙烯酸和乙酸.图2参5 国家自然科学基金(29676007)资助 O643 01050229 用以分解氟里昂-12的新型催化剂WO3/Al2O3=A Novel Catalyst WO3/Al2O3 for Decomposition of CFC-12[刊, 中]/马臻(复旦大学),华伟明…∥应用化学.&2000, 17(3).&319~321 国家科委攀登计划资助 O643 01050230 LaFeO3的光催化性=Photocatalytic Activity of LaFeO3[刊, 中]/白树林(天津大学),付希贤…∥应用化学.&2000, 17(3).&343~345 采用柠檬酸法和微乳液法制备纳米晶LaFeO3.结果表明,微乳液法较柠檬酸法制备的LaFeO3粒径小,表面积大,使LaFeO3吸附性增加,因此表现出较强的光催化活性.图2表1 国家自然科学基金(59772019)资助 O643 01050231 NiO/SiO2催化剂上CO氧化的反应机理研究=Mechanism of CO Oxidation on NiO/SiO2 Catalyst[刊, 中]/王远洋(宁夏大学),高荫本…∥宁夏大学学报(自然科学版).&2000, 21(2).&147~149 NiO/SiO2是优良的非贵金属型CO氧化催化剂,EXAFS和TPR表征表明其活性中心为NiO.在此基础上的Monte Carlo模拟表明,在NiO/SiO2上CO氧化遵循L-H机理.图5参11 国家自然科学基金(29803009)资助 O643 01050232 烯基取代的茂钛族络合物合成及应用于烯烃催化聚合的进展=Recent Advances in the Synthesis of Alkenyl Substituted Metallocene Complexes(Ti,Zr,Hf) and the Application of Its to α-Olefins Polymerization[刊, 中]/钱贤苗(华东理工大学),许胜…∥功能高分子学报.&2000, 13(3).&358~366 综述了含烯基取代基的茂钛族络合物的合成,取代基上双键的化学反应,以及在α-烯烃催化聚合上的最新进展.表2参45 国家自然科学基金(29871010)资助 O643 01050233 氧化态Co/γ-Al2O3催化剂的结构与反应性能研究:Ⅱ.钴物种微观结构的XAFS表征=Studies on the Structures and Catalytic Properties of Oxidized Co/γ-Al2O3 Catalysts:Ⅱ.XAFS Characterizations of the Micro-Structures of Co Species[刊, 中]/孟明(中国科学技术大学),林培琰…∥分子催化.&2000, 14(3).&161~165 采用X-射线吸收近边结构与扩展X-射线吸收精细结构技术,对用不同原料盐和不同焙烧温度制得的Co/γ-Al2O3催化剂中钴的微观结构进行了详细的表征.图5表1参8 国家自然科学基金(29973037)资助 O643 01050234 CuCl/γ-Al2O3上NO脱除过程研究=Reaction Mechanism of NO Conversion over CuCl/γ-Al2O3[刊, 中]/朱月香(北京大学),尉继英…∥分子催化.&2000, 14(3).&166~170 设计了一系列的对比实验,利用XRD、XPS、TPR、EXAFS等技术,系统研究了CuCl/γ-Al2O3上的NO脱除反应过程.图4表1参8 国家自然科学基金(29733080)资助 O643 01050235 以Au(PPh3)(NO3)为前体的Au/NiO催化剂的制备及其对CO的催化氧化=Preparation and Catalytic Performance of Au/NiO Catalyst Derived from Au(PPh3)(NO3) for CO Oxidation[刊, 中]/邹旭华(烟台大学),齐世学…∥分子催化.&2000, 14(3).&171~174 采用有机金属配合物固载法,将金的有机配合物Au(PPh3)(NO3)沉积于刚制备出的Ni(OH)2沉淀上.结果表明,以K2CO3作为制备Ni(OH)2的沉淀剂,金担载量为3%(质量分数)在焙烧温度为300℃的条件下,制备出的负载型金催化剂Au/NiO对CO的低温氧化有很高的催化活性.图2表3参15 国家自然科学基金(29873041)资助 O643 01050236 CexZr1-xO2复合氧化物负载PdO催化剂的CO和CH4氧化性能研究=CO and Methane Oxidation over CexZr1-xO2 Mixed Oxide Supported PdO Catalysts[刊, 中]/马磊(浙江大学),韩立峰…∥分子催化.&2000, 14(3).&175~178 浙江省自然科学基金资助 O643 01050237 溶胶-凝胶法镍基催化剂的研究&&Ti/Si原子比对NiO-TiO2-SiO2结构和苯加氢性能的影响=Study of the Nickel Catalysts Prepared by Sol-Gel Method&&The Effects of Si/Ti Atomic Ratios on the Structure and Catalytic Performance for Benzene Hydrogenation of NiO/TiO2-SiO2[刊, 中]/朱毅青(江苏石油化工学院),林西平…∥分子催化.&2000, 14(3).&184~190 中石化集团公司资助课题 O643 01050238 (NH4)15[La(PMo9V2O39)2]*6H2O杂多配合物对苯酚羟化的催化作用=Catalytic Activity of (NH4)15[La(PMo9V2O39)2]*6H2O Heteropoly Complex in Phenol Hydroxylation with Hydrogen Peroxide[刊, 中]/林深(福建师范大学),郑瑛…∥分子催化.&2000, 14(3).&191~194 福建省科委资助项目 O643 01050239 Co改性Mo/HZSM-5催化剂上甲烷无氧芳构化反应研究=Methane Dehydro-Aromatization over Cobalt Modified Mo/HZSM-5 Catalysts in the Absence of Oxygen[刊, 中]/田丙伦(中科院大连化学物理所),刘红梅…∥分子催化.&2000, 14(3).&200~204 国家重点基础研究发展规划项目 O643 01050240 甲醇催化氧化重整反应制氢的研究=Hydrogen Production by Catalytic Oxidation and Reforming of Methanol[刊, 中]/陈兵(华南理工大学),董新法…∥分子催化.&2000, 14(3).&205~208 广东省高教厅自然科学基金资助 O643 01050241 TiO2催化Cr(Ⅵ)-氯代苯酚共存体系中Cr(Ⅵ)的光致还原=Photo-Induced Cr(Ⅵ) Reduction in Cr(Ⅵ)-4CP Coexist Pollution System in the Presence of TiO2 Photocatalyst[刊, 中]/付宏祥(中科院兰州化学物理所),吕功煊…∥分子催化.&2000, 14(3).&214~218 中科院重大项目资助 O643 01050242 三磺化三苯基膦(TPPTS)制备方法的改进=Improvement of Synthesis Method of TPPTS[刊, 中]/张敬畅(北京化工大学),曹维良…∥分子催化.&2000, 14(3).&223~226 国家"九五”科技攻关项目 O644 01050243 预处理对TiO2表面超亲水性的影响=Effect of Pretreatment on Superhydrophilicity of TiO2 Films[刊, 中]/管自生(中科院化学所),马颖∥感光科学与光化学.&2000, 18(3).&204~207 在高温度环境下,应用紫外光辐射对溶胶-凝胶TiO2薄膜预处理,经过预处理的薄膜烧结后具有快速光致高度亲水特性和良好的光催化活性.超亲水的薄膜能够吸附大量的酸性品红,在光照下薄膜将吸附的酸性品红逐渐降解掉.图3参6 国家自然科学基金(59932040)重点资助 O644 01050244 荧光探针在测定N-异丙基丙烯酰胺共聚物最低临界溶液温度(LCST)时的扩散过程=The Diffusion Process of Fluorescence Probe in Measurement of LCST of Poly(N-Isopropylacrylamide-co-Acrylamide) Aqueous Solution[刊, 中]/李俊(中科院感光化学所),史向阳∥感光科学与光化学.&2000, 18(3).&208~213 合成了多种不同配比的N-异丙基丙烯酰胺(NIPAM)与丙烯酰胺(AM)的共聚物.研究了共聚物溶液在温度变化过程中发生的线团-胶粒转变,及荧光探针分子扩散进入疏水胶粒的动力学过程.图3表2参9 国家自然科学基金(29733100)资助 O644 01050245 蒽醌冠醚铕离子络合物分子内能量转移=Intramolecular Energy Transfer in Anthraquione Crown Ether-Eu3+ Complex[刊, 中]/江华(中科院感光化学所),许慧君∥感光科学与光化学.&2000, 18(3).&223~228 研究结果表明,选择性激发铕离子络合物中的蒽醌冠醚能发生分子内能量转移,观察到铕离子的发光.荧光衰减测试表明,由于冠醚的包络作用使得铕离子络合物的荧光寿命较未络合铕离子的寿命有所延长.图5表1参10 国家自然科学基金(29733100)资助 O644 01050246 有机染料光褪色机理及主要原因=The Mechanism and Main Reasons of Photofading of Organic Dyes[刊, 中]/于新瑞(大连理工大学),张淑芬∥感光科学与光化学.&2000, 18(3).&243~253 综述了有机染料光褪色机理的主要研究方法以及现有研究结论.对光氧化和光还原过程、影响因素、典型反应步聚、研究手段进行了系统的阐述,同时也对通过染料分子结构设计合成、通过添加剂的使用提高染料光牢度的方法进行了介绍.图4表3参29 国家自然科学基金重点基金(29836150)资助 O644 01050247 荧光分子开关的研究进展=The Progress of the Research on Fluorescent Molecular Switches[刊, 中]/甘家安(华东理工大学),陈孔常∥感光科学与光化学.&2000, 18(3).&254~262 根据开关动作完成的方式对近年来研究的各类荧光分子开关进行了简要的归类总结,并介绍了一些具有特殊功能的荧光分子开关器件.图8参33 国家自然科学基金(29836150)资助 O644 01050248 半花菁衍生物LB膜的光致荧光特性研究=Photoluminescence Characteristics of Hemicyanine Derivatives in Langmuir Blodgett Multilayers[刊, 中]/王文军(复旦大学),陆兴泽…∥物理化学学报.&2000, 16(6).&496~500 通过改变半花菁的亲水基团与硫水基团而得到了四种半花菁衍生物,利用稳态和时间分辨荧光研究了不同亲水基团与疏水基团对半花菁衍生物光学特性的影响.图1表3参7 国家自然科学基金重点基金(19834030)资助 O644 01050249 N-萘甲基多乙撑多胺类荧光化学敏感器=Fluorescence Chemical Sensor of Naphthylmethyl Polyethylenepolyamine[刊, 中]/梅明华(中科院感光化学所),吴世康∥物理化学学报.&2000, 16(6).&559~562 合成了一类带有萘甲基的多乙撑多胺化合物,对其在不同溶剂中作为FCS检测锌离子时的荧光光谱变化进行了研究.结果表明,两种不同锌盐化合物与配体相互作用时,其所带阴离子对络合物的组成和方式有很大的影响.图2表1参6 国家自然科学基金(29733100)资助 O644 01050250 三聚氰胺甲醛树脂的光学性质=Optical Properties of Melamine Formaldehyde Resin[刊, 中]/刘海波(复旦大学),侯占佳…∥物理化学学报.&2000, 16(6).&563~567 对三聚氰胺甲醛树脂的合成过程、波导制备条件及利用三聚氰胺甲醛树脂作为掺杂基质的非线性光学性质进行了研究.实验结果表明,三聚氰胺甲醛树脂是一种极具有应用前景的光学材料.图3参14 国家自然科学基金(69708005,69808001)资助 O644 01050251 紫菜两个光系统间激发能分配研究对光合进化的启示[刊, 中]/潘洁(中科院化学所),施定基…∥科学通报.&2000, 45(12).&1276~1279 选择两个不同发育阶段(孢子体和配子体)的条斑紫菜作为研究对象.对过多激发能在两个光系统间的分配进行了比较研究.图2参13 国家自然科学基金(39890390,29733100)资助 O644 01050252 非线性光学配合物的化学研究[刊, 中]/左景林(南京大学),游效曾∥科学通报.&2000, 45(14).&1457~1464 从化学角度出发,在分子水平上研究和探索新型分子基非线性光学材料是一个新的研究领域.总结了近年来在新型二阶、三阶极化率和光限制等非线性光学配合物的化学研究方面所取得的进展.图6表2参46 国家自然科学基金(29631040)资助 O644 01050253 螺旋共轭化合物1′,3′,3′-三甲基-6-羟基螺旋[2H-1-苯并吡喃-2,2′-二氢吲哚]的结构、光谱、非线性光学性质和光异构化过程的理论研究=Theoretical Study of the Structures, Spectra, Nonlinear Second-Order Optical Properties and Photoisomerization Process of the Spiroconjugated Compound 1′,3′,3′-Trimethyl-6-Hydroxyspiro[2H-1-Benzopyran-2,2′-Indoline][刊, 中]/孙秀云(吉林大学),封继康…∥高等学校化学学报.&2000, 21(7).&1080~1085 用AM1和ZINDO方法研究了螺旋共轭化合物1′,3′,3′-三甲基-6-羟基螺旋[2H-1-苯并吡喃-2,2′-二氢吲哚](HBPS)及其光导构化产物的结构和光谱性质,从理论上研究了HBPS的光异构化反应过程,并在此基础上,用自编的完全态求和公式(SOS)程序计算了非线性光学系数.图4表7参17 国家自然科学基金(29873016)资助 O644 01050254 Af型自由基均聚反应的固化理论(Ⅲ)&&高分子凝胶网络缺陷=The Curing Theory of Af Type Free Radical Homopolymerization(Ⅲ)&&The Defects of Polymer Gel Network[刊, 中]/王海军(河北大学),赵敏…∥高等学校化学学报.&2000, 21(7).&1138~1141 应用高分子反应统计理论,分析了高分子网络的形成过程,讨论了Af型自由基均聚反应凝胶网络中的缺陷&&悬吊环的数目及其形成几率.图4参22 国家自然科学基金(29673018)资助 O646 01050255 微过氧化物酶-11修饰电极对O2和H2O2的电催化还原=Electrocatalytic Reduction of O2 and H2O2 at the Glass Carbon Electrode Modified with Microperoxidase-11[刊, 中]/杨辉(南京师范大学),黄志忠…∥物理化学学报.&2000, 16(6).&527~532 运用电化学循环伏安法和旋转圆盘电极技术研究了O2和H2O2在Nafion膜固定的微过氧化物酶-11修饰的玻碳电极上的电化学还原.图6参16 国家自然科学基金资助 O646 01050256 电沉积Co-Cu颗粒膜的巨磁电阻效应=Giant Magnetoresistance in Electro-Deposited Co-Cu Granular Film[刊, 中]/李浩华(兰州大学),黎超…∥物理化学学报.&2000, 16(6).&573~576 用电化学沉积法制备了Co-Cu纳米颗粒膜,并对这种膜的结构、磁性、巨磁电阻效应作了较详细的研究.图6参7 国家自然科学基金资助 O646 01050257 磷酸溶液中铝恒压阳极氧化的研究=Investigation of Aluminum Anodizing in Phosphoric Acid Solution at Constant Voltage[刊, 中]/王为(天津大学),郭鹤桐…∥天津大学学报.&2000, 33(3).&341~343 结果表明,随着电解电压的升高,形成的氧化铝多孔膜的阻挡层增厚,多孔层的孔径和胞径均增加,其原因与离子迁移等密切相关.图6参6 国家自然科学基金(69601006)资助 O646 01050258 二次微分简易示波伏安法测定痕量镍=Determination of Trace Nickel by Second-Order Differential Simple Oscillographic Voltammetry[刊, 中]/傅业伟(西北大学),高敏…∥应用化学.&2000, 17(3).&296~299 国家自然科学基金(29775018)资助 O646 01050259 Ml(NiCuAlZn)5储氢合金粉末的包覆处理=Encapsulation of Ml(NiCuAlZn)5 Hydrogen Storage Alloy Powder[刊, 中]/王一菁(南开大学),赵东…∥应用化学.&2000, 17(3).&310~312 国家"八六三”计划资助项目 O646 01050260 和厚朴酚电化学还原机理的研究=Theoretical Study on the Mechanism of Electrochemical Reductions Reaction of Honokiol[刊, 中]/孙成科(曲靖师范高等专科学校),龚思源…∥高等学校化学学报.&2000, 21(6).&912~917 用量子化学AM1、PM3方法研究了和厚朴酚分子的电化学还原反应机理.结果表明,和厚朴酚分子电还原的基团为两个烯丙基的双键,其中邻位烯丙基优先被还原,对位次之,整个还原反应中和厚朴酚得到4e和4H+,使两个烯丙基饱和,计算结果较好地说明了实验事实.图2表7参12 国家自然科学基金(29773007)资助 O646 01050261 Fourier自去卷积示波计时电位法的研究=Oscillographic Chronopotentiometry with Fourier Self-Deconvolution[刊, 中]/郑建斌(西北大学),张红权…∥高等学校化学学报.&2000, 21(7).&1037~1039 国家自然科学基金(29775018)资助 O646 01050262 用规整膜板对砷化镓的三维微结构图形加工刻蚀=Three-Dimensional Microfabrication on GaAs Using a Regular Patterns Mold[刊, 中]/董海苟(厦门大学),孙建军…∥电化学.&2000, 6(3).&253~257 以微齿轮图形结构作为规整模板.用约束刻蚀剂层技术对GaAs样品表面进行了加工刻蚀.在有捕捉剂H3AsO3存在的情况下,规则微齿轮图形能够很好地在样品表面复制.图5参6 国家自然科学基金重点项目(29833070)资助 O646 01050263 混凝土中钢筋的腐蚀行为研究=Corrosion Behavior of Reinforcing Steel in Concrete[刊, 中]/林荣归(厦门大学),胡融刚…∥电化学.&2000, 6(3).&305~310 钢筋在混凝土中受到高碱性环境的保护,耐蚀性好,但随着介质pH的降低、Cl-含量的上升,钢筋腐蚀电流升高;动电位阳极极化曲线的测试表明,钢筋的维钝电流增大,击穿电位负移,混凝土中钢筋的耐蚀性下降.图4表1参6 国家自然科学基金(59871043)资助 O647 01050264 天冬氨酸在Cu(001)表面吸附的扫描隧道显微镜研究=Adsorption of Aspartic Acid on Cu(001) Studied by Scanning Tunneling Microscopy[刊, 中]/王浩(北京大学),赵学应…∥物理学报.&2000, 49(7).&1316~1320 国家自然科学基金(19634010)资助 O647 01050265 共聚高分子吸附的Monte Carlo模拟=Monta Carlo Simulation of Adsorption of Diblock Copolymer at Solid-Liquid Interface[刊, 中]/陈霆(华东理工大学),刘洪来…∥化工学报.&2000, 51(4).&512~518 用Monte Carlo方法对选择性溶剂中两嵌段共聚高分子在固液界面的吸附进行了模拟,获得了吸附等温线以及吸附层厚度、链附着率、表面覆盖率、链节浓度分布等表征吸附层结构的信息,同时模拟获得了固液界面区吸附构型大小及分布等表征高分子构型的微观信息.图12表1参10 国家自然科学基金(29736170)资助 O647 01050266 无规共聚高分子溶液相平衡的Monte Carlo模拟=Monte Carlo Simulations of Phase Equilibria of Random Copolymer Solutions[刊, 中]/陈霆(华东理工大学),刘洪来…∥化工学报.&2000, 51(4).&552~554 用构型偏倚蒸发Monte Carlo方法模拟研究了密堆积格子模型上A、B无规共聚高分子的相平衡问题,无规共聚高分子中链节A、B以不同的相互作用能来区别.模拟获得了链长直至200个链节的无规共聚高分子系统相平衡数据,同时计算获得了不同链长固定组成下无规共聚高分子系统相应的临界点.图2表1参12 国爱自然科学基金(29736170)资助 O648 01050267 Triton X-100/正癸醇/水层状液晶制备泡囊=Preparation of Vesicles from Lamellar Liquid Crystal in Triton X-100/n-C10H21OH/H2O System[刊, 中]/丁元华(扬州大学),刘天晴…∥物理化学学报.&2000, 16(6).&481~486 以Triton X-100/n-C10H21OH/H2O体系生成的层状液晶为介质制备泡囊,所得泡囊分布比较均匀,囊径在0.2~0.5 μm之间.研究了层状液晶组成、pH、超声振荡时间等因素对所制泡囊的电位及微极性的影响.图6表2参16 国家自然科学基金(29673035)资助 O648 01050268 表面波技术研究TBP对C12E8表面流变性质的影响=Influence of TBP on the Surface Rheological Properties of C12E8 Studied by Surface Wave Method[刊, 中]/韩国彬(厦门大学),吴金添…∥物理化学学报.&2000, 16(6).&507~511 利用表面波技术研究消泡剂TBP对起泡剂C12E8表面流变性质的影响,阐述泡沫的排液过程中液膜变形所产生的表面张力梯度修复机理以及液膜强度与表面膨胀模量、表面膨胀弹性和表面膨胀粘度的关系,并且探讨了消泡剂TBP的消泡机理.图4参6 国家自然科学基金(29973033)资助 O648 01050269 制备宽温区O/W微乳的新方法=Novel Method to Prepare O/W Microemulsions within a Wide Temperature Range[刊, 英]/梁文平(中科院化学所),Tharwat F Tadros∥物理化学学报.&2000, 16(6).&538~542 通过把一个带有羧基的离子表面活性剂镶嵌在微乳界面的单分子层中,在低pH值时,形成水包油微乳,然后用氢氧化钠中和使其表面离子化而形成一个较厚的双电层,从而得到的宽温区(0-90℃)水包油微乳.研究了油相浓度、pH以及微乳液滴的大小对体系的浊点的影响.图5参12 国家自然科学基金资助 O65 01050270 Triton X-100与牛血清白蛋白的相互作用=The Interaction between Triton X-100 and Bovine Serum Albumin[刊, 中]/魏晓芳(中科院化工冶金所),刘会洲∥分析化学.&2000, 28(6).&699~701 国家自然科学基金重点项目资助 O65 01050271 球形铜离子模板缩聚物的制备及其选择吸附性能=The Preparation of Globular Copper(Ⅱ) Template Condensation Polymer and Its Behavior of the Selective Adsorption[刊, 中]/王旭东(南开大学),何锡文…∥分析化学.&2000, 28(7).&805~809 以苯酚、甲醛、四乙烯五胺为反应单体,铜离子为模板,反相悬浮聚合制备出球形离子模板缩聚物.该模板缩聚物对铜离子的吸附性能显著优于相应的非模板缩聚物.图6参3 国家自然科学基金(29775011)资助 O65 01050272 杯芳烃银离子敏感场效应晶体管传感器=Silver Ion-Sensitive Field-Effect Transistor Based on Calixarene[刊, 中]/陈朗星(南开大学),牛文成…∥分析化学.&2000, 28(7).&815~819 报道了硫醚取代的杯[4]芳烃化合物的合成,以此化合物为敏感材料,研制了聚氯乙烯膜的银离子敏感场效应晶体管(Ag+-ISFET)传感器.Ag+-ISFET传感器对银离子表现出优良的能斯特响应,该传感器对碱金属、碱土金属及过渡金属离子有极高的选择性.图5表1参13 国家自然科学基金(29975014)资助 O65 01050273 电极扩散层内物质浓度及分布研究方法进展=Development of Research Method of Concentration Observation and Distribution in Electrode Diffusion Layer[刊, 中]/杨玉书(重庆大学),夏之宁…∥分析化学.&2000, 28(7).&897~903 评述了测试电极扩散层内物质浓度及分布的各种方法,分别从方法原理、实验装置、影响因素及其应用等方面加以论述,评价了各种方法的特点,并对发展方向进行了展望.参52 国家自然科学基金(29775035)资助 O657 01050274 甲烷氧化偶联Na-W-Mn/SiO2催化剂的喇曼光谱=Raman Spectroscopy Characterization of Na-W-Mn/SiO2 Catalyst for Oxidative Coupling of Methane[刊, 中]/陈宏善(中科院兰州化学物理所),牛建中…∥物理化学学报.&2000, 16(6).&543~546 研究了A16061/SiCp复合材料表面双层稀土转化膜的微观结构以及化学组成,并对稀土转化膜对抗腐蚀性能进行了评估.结果表明,稀土转化膜能显著提高耐蚀性.图2表3参10 国家自然科学基金资助 O657 01050275 12-钼磷酸-葡聚糖包合物的研究=Study on the Inclusion Compound of 12-Molybdenum Phosphoric Acid with Dextran[刊, 中]/程贤C026(福建师范大学),苏英草…∥物理化学学报.&2000, 16(7).&658~662 福建省教委基金资助 O657 01050276 O/W微乳液中制备甲基丙烯甲酯-苯乙烯共聚物超细颗粒=Preparation of Methyl Methacrylate and Styrene Copolymer Ultrafine Particles in the Oil-in-Water Microemulsions[刊, 中]/钱君律(同济大学),甘礼华…∥同济大学学报(自然科学版).&2000, 28(3).&320~323 在甲基丙烯酸甲酯(MMA)-苯乙烯-环己烷/十六烷基三甲基溴化铵/水体系的O/W微乳液中,制备了粒径约58 nm球状甲基丙烯酸甲酯-苯乙烯共聚物超细颗粒.研究了影响粒子形态和大小的因素.图4表1参12 国家自然科学基金(29673030)资助 O657 01050277 基于小波神经网络的新型算法用于化学信号处理=A Novel Algorithm Based on the Wavelet Neural Network for Processing Chemical Signals[刊, 中]/蔡文生(中国科技大学),于芳…∥高等学校化学学报.&2000, 21(6).&855~859 基于紧支集正交小波神经网络的构造思想,用具有紧支集的B-样条函数的伸缩和平移替代小波函数,提出了一种新型算法,并将其应用于化学信号的处理,实现了信号的压缩和滤噪,与自适应小波神经网络相比,学习速度得到了大幅度的提高.图4表2参9 国家自然科学基金(29775001)资助 O657 01050278 改进溶胶-凝胶法固定酶结构剖析及在苯酚光化学传感器中的应用=The Microstructure Analysis of Enzymes Immobilized by Sol-Gel Method and Its Application in Phenol Optical Chemical Sensor[刊, 中]/李军(湖南大学),王柯敏…∥高等学校化学学报.&2000, 21(7).&1018~1022 结果表明,酶固定于溶胶-凝胶中后,与在溶液中一样,呈均匀分布且不易流失.此敏感膜可用于制备基于化学发光强度减弱的苯酚光化学传感器;用竞争反应的原理讨论了响应机理.图3表1参20 国家自然科学基金(29675005)及国家杰出青年基金(29825110)资助 O657 01050279 一种用于电热蒸发-原子光谱的微型化固相萃取技术=A Miniaturization Solid-Phase Extraction Technique Designed for Electrothermal Vaporization-Atomic Emission Spectrometry Determination[刊, 中]/熊宏春(武汉大学),胡斌…∥高等学校化学学报.&2000, 21(7).&1035~1036 国家自然科学基金(29875022)资助 O657 01050280 多环芳烃芴、苊的无保护流体室温磷光性质研究=Studies on Non-Protected Fluid Room Temperature Phosphorescence of Polycyclic Aromatic Hydrocarbon of Fluoren and Acenaphthene[刊, 中]/李隆弟(清华大学),牟兰…∥高等学校化学学报.&2000, 21(7).&1040~1042 国家自然科学基金(29775013)资助 O657 01050281 高效液相色谱/大气压化学电离质谱快速分析水中痕量有机磷农药=Rapid Analysis of Trace Organophosphorous Pesticides in Water by High Performance Liquid Chromatography/Atmospheric Pressure Chemical Ionization Mass Spectrometry[刊, 中]/潘元海(中科院生态环境研究中心),金军…∥分析化学.&2000, 28(6).&661~671 用反相液谱短柱实现了6种有机磷农药(乙酰甲胺磷,甲基对硫磷、杀螟硫磷、喹硫磷、二嗪农、辛硫磷)的高效液相色谱/大气压化学电离质谱(HPLC/APCIMS)快速分析.此技术可以很好地实现水中痕量有机磷农药的测定,一次联机分析仅需10 min.图3表2参11 国家自然科学基金(29977023)资助 O657 01050282 氧氟沙星对映体的同步-导数荧光光谱法识别与测定=Recognition and Determination of Ofloxacin Enantiomers by Synchronization-Derivative Fluorimetry[刊, 中]/弓巧娟(山西大学),晋卫军…∥分析化学.&2000, 28(6).&672~677 控制pH=3,首次通过同步一阶导数荧光光谱技术,有效地识别和分辨氧氟沙星的R和S对映体,同时有效地消除尿样背景的干扰.据此建立了同时识别与测定两种旋光体的同步-导数荧光光谱法.图5表2参9 国家自然科学基金(29875016)资助 O657 01050283 一种新的重原子微扰剂氯代叔丁烷在亚硫酸钠化学除氧环糊精诱导室温磷光法中的应用研究=A Study of t-Butyl Chloride as Heavy Atom Perturber in Chemical Deoxygenation-Cyclodextrin Induced Room Temperature Phosphorimetry[刊, 中]/张淑珍(山西大学),魏雁声…∥分析化学.&2000, 28(6).&678~681 以氯代叔丁烷作重原子微扰剂采用亚硫酸钠化学除氧技术建立了菲、7,8-苯并喹啉、2-溴代萘在环糊精介质中的室温磷光分析法.图4表2参5 国家自然科学基金(29575204)资助 O657 01050284 小牛胸腺脱氧核糖核酸诱导中性红聚集的机理及其影响因素=The Aggregation of Neutral Red Encouraged by Deoxyribonucleic Acids and Its Depending Factors[刊, 中]/黄新华(西南师范大学),李原芳…∥分析化学.&2000, 28(6).&682~686 在pH7.6~7.8和低离子强度条件下,中性红与小牛脱氧核糖核酸(ctDNA)作用产生以535 nm为特征的共振光散射增强(ERLS)光谱.机理研究表明,这种ERLS是由于DNA诱导中性红的聚集所致.图6表1参11 国家自然科学基金(29875019)资助 O657 01050285 蛋白质样品的非竞争性毛细管电泳免疫分析激光诱导荧光检测=Noncompetitive Capillary Electrophoresis Based Immunoassay for Proteins with Laser Induced Fluorescence Detection[刊, 中]/王清刚(清华大学),罗国安…∥分析化学.&2000, 28(6).&687~691 国家自然科学基金重点资助 O657 01050286 亲和毛细管电泳测定孕酮与其单克隆抗体的结合常数=Determination of the Binding Constant between Progesterone and Its Monoclonal Antibody Using Affinity Capillary Electrophoresis[刊, 中]/王清刚(清华大学),王义明…∥分析化学.&2000, 28(6).&731~734 采用亲和毛细管电泳的配体分离模式,以激光诱导荧光作为检测手段,测定了荧光素标记的孕酮与孕酮单克隆抗体之间的结合常数,并研究了温育时间、电泳条件等因素对测定的影响.图3参5 国家自然科学基金重点资助 O657 01050287 钌(Ⅱ)-联吡啶-铈(Ⅳ)-戊二醛化学发光体系及其应用=Chemiluminescence System of Ru(bpy)2+3-Ce(Ⅳ)-Glutaraldehyde and Its Application[刊, 中]/韩鹤友(武汉大学),何治柯…∥分析化学.&2000, 28(6).&738~740 基于在硫酸介质中戊二醛增强铈(Ⅳ)氧化钌(Ⅱ)-联吡啶的化学发光强度.在优化后的条件下,方法的线性范围和检测限分别为2.5×10-6~2.5×10-3 mol/L和3.1×10-7 mol/L戊二醛.图1表1参6 国家自然科学基金(29605001)资助 O657 01050288 毛细管区带电泳法测定甲氧苄胺嘧啶和磺胺甲基异C023唑的离解常数及其在复方新诺明中的含量=Determination of Dissociation Constants of Trimethoprim and Sulfamethoxazole and Their concentrations in Co-Trimoxazole Tablets by Capillary Zone Electrophoresis[刊, 中]/李前锋(兰州大学),张红医…∥分析化学.&2000, 28(7).&793~797 国家自然科学基金(29475194和29675007)资助 O657 01050289 联用色谱数据的半自动解析法=Semiautomatic Deconvolution of Hyphenated Chromatographic Data[刊, 中]/甘峰(湖南大学),李晓宁…∥分析化学.&2000, 28(7).&833~836 采用正交投影法获得初始迭代光谱,继采用非负最小二乘法和常规最小二乘法进行交替迭代,最终获得纯光谱和纯色谱向量.图2参15 国家自然科学基金(29875007)资助 O657 01050290 陈皮挥发油的气相色谱/质谱分析=Determination of the Volatile Oil of Pericarpium Citri Reticulatae with Gas Chromatography/Mass Spectrometry[刊, 中]/龚范(湖南大学),梁逸曾…∥分析化学.&2000, 28(7).&860~864 用GC/MS分析复方制剂平胃散中的一种单味药材陈皮的挥发油化学成分及其相对含量.分离出53个组分,其中鉴定了34个组分,约占其挥发油总量的96.08%.图5表1参7 国家自然科学基金(29875007)资助 657 01050291 人工神经网络法鉴别红外光谱=Artificial Neural Network for the Identification of Infrared Spectra[刊, 中]/李燕(南京理工大学),王俊德…∥光谱学与光谱分析.&2000, 20(4).&477~479 将反向传播人工神经网络用于FTIR,鉴别未知化合物.结果表明,当训练集样本不含噪声时,纯光谱的预测结果很好.而当训练集样本有少量噪声干扰时,预测结果随预测集样本的不同,而得到了不同的改善.图3参6 国家自然科学基金资助 O657 01050292 苯丙氨酸桥联金属双卟啉的诱导圆二色光谱研究=The Study of Induced Circular Dichroism of Phenylalanine Bridged Metal Bis-Porphyrin[刊, 中]/刘海洋(华南理工大学),黄锦汪…∥光谱学与光谱分析.&2000, 20(4).&495~497 报道了邻位和对位桥联苯丙氨酸锌双卟啉的合成,考查了双卟啉的分子结构对诱导圆二色性的影响.结果表明,两个卟啉环之间的π-π堆积和手性激子偶合作用是影响此类双卟啉圆二色光谱的主要因素.图3参16 国家自然科学基金(29771034)资助 O657 01050293 砷和汞的顺序注射-蒸气发生原子吸收光谱测定=Sequential Injection Vapor Generation Atomic Absorption Spectrometric Determination of Mercury and Arsenic[刊, 中]/马泓冰(东北大学),徐淑坤…∥光谱学与光谱分析.&2000, 20(4).&529~532 建立了砷和汞的顺序注射-蒸气发生原子吸收光谱测定方法.在流动注射蒸气发生原子吸收光谱测定方法的基础上,采用汇流技术,通过两个微量注射泵和一个多位选择阀的计算机程控操作,实现待测组分与硼氢化钠间的强氧化还原反应及其气-液分离过程.图3表4参4 国家自然科学基金资助 O657 01050294 氢化物的气相富集及其在超痕量分析中的应用=The Gaseous Phase Enrichment Techniques in Hydride Generation (Review)[刊, 中]/郭旭明(厦门大学),黄本立…∥光谱学与光谱分析.&2000, 20(4).&533~536 从富集原理及其在光谱超痕量分析的应用方面分别对这几种氢化物发生后的气相富集技术进行了较详细地综述.这些气相富集方法包括液氮冷却捕集技术、气球收集技术、石墨炉原位捕集技术、吸收液吸收技术及固体吸附技术等.参63 国家自然科学基金资助 O657 01050295 pH诱导牛血清白蛋白芳香氨基酸残基微环境变化的光谱分析=Spectral Study of the Microenviroment Change of Aromatic Amino-Acid Residues in BSA Induced by pH[刊, 中]/魏晓芳(中科院化工冶金所),刘会洲…∥光谱学与光谱分析.&2000, 20(4).&556~559 用荧光光谱和紫外吸收光谱研究了pH=2.3~11.3范围内牛血清白蛋白芳香氨基酸残基微环境的变化,以此推断蛋白质构象的变化,并讨论蛋白质表面疏水性变化的趋势.图4表1参8 国家自然科学基金重点基金资助 O657 01050296 传感器几何结构对近红外组织氧合检测仪灵敏度的影响=The Influence of Probe Geometry on the Sensitivity of Tissue Oximeter Using Near Infra-Red Spectroscopy[刊, 中]/王峰(清华大学),丁海曙…∥光谱学与光谱分析.&2000, 20(4).&585~588 利用蒙特卡罗仿真方法对光在多层生物组织模型中的平均穿透深度、光子平均飞行距离和空间灵敏度分布进行了仿真,结果表明,传感器几何结构,即光源与光检测器之间的距离是影响灵敏度的重要因素,适当增加这一距离有助于深层组织生化信息的提取和测量灵敏度的提高,但是它又受到信噪比降低的限制.图8参3 国家自然科学基金资助 O657 01050297 精密气动液压伺服系统用于傅里叶变换光谱仪光谱测量=Spectral Measuring of Fourier Transform Spectrometer Using Pneumatic Hydraulic Servo System[刊, 中]/李志刚(中科院长春光学精密机械所),王淑荣…∥光谱学与光谱分析.&2000, 20(4).&589~591 讨论了傅里叶变换光谱仪动镜稳定平移的重要性,研制了以高压无氧氮气为动力源的精密气动液压系统用于推进在研傅里叶变换光谱仪"猫眼”动镜系统,并在此基础上测量了ZYGO干涉仪光源光谱图.图4参5 国家自然科学基金资助 O658 01050298 超临界流体色谱法分离手性化合物的进展=Advances in Chiral Separations by Supercritical Fluid Chromatography[刊, 中]/任其龙(浙江大学),苏宝根…∥分析化学.&2000, 28(6).&772~776 国家自然科学基金(29776040)资助 O658 01050299 长江口水体混合过程中溶解态稀土元素分布特征[刊, 中]/王中良(中科院地球化学所),刘丛强∥科学通报.&2000, 45(12).&1322~1326 采用液-液萃取与反萃取分离富集方法和ICP-MS测试技术,对长江河口南支盐度0.15~19 mg/g表层水体中溶解态稀土元素的浓度进行了测定.图2表1参17 国家杰出青年科学基金(49625304)资助 O658 01050300 分子烙印手性固定相分离过程热力学研究=Thermodynamic Study on Separation of Molecular Imprinting Chiral Stationary Phase[刊, 中]/王进防(中科院大连化学物理所),周良模…∥高等学校化学学报.&2000, 21(6).&930~933 结果表明,分子烙印手性固定相的分离过程为焓控制过程.随着温度的升高,样品的容量因子降低,手性选择因子α减小.样品与分子烙印固定相的作用力包括非特异作用力和特异作用力,只有特异作用力的差值才是手性分离的本质.表2参22 国家自然科学基金(29575212)资助 O658 01050301 十八烷基醚型高效液相反相色谱填料的制备=Synthesis and Characterization of Ether-Bond RP-Packing[刊, 中]/喻昕(中科院化学所),赵睿…∥高等学校化学学报.&2000, 21(7).&1043~1044 国家自然科学基金(29635010)资助