Professeur des Universités, Sorbonne Université
Responsable du pôle de Chimie Physique et Biologique de la Matière Vivante
PASTEUR, Département de chimie, École Normale Supérieure, PSL University, Sorbonne Université, CNRS
24 rue Lhomond, 75005 Paris, France
Email: Ludovic.Jullien@ens.psl.eu or Ludovic.Jullien@sorbonne-universite.fr
Phone: +33 144323333
Office: E142c
Home page: https://ludovicjullien.org/
Publications
1999 |
Self-assembly of Janus cyclodextrins at the air-water interface and in organic solvents Article de journal B Hamelin; L Jullien; A Laschewsky; C Hervé Du Penhoat Chemistry - A European Journal, 5 (2), p. 546–556, 1999. @article{Hamelin:1999, title = {Self-assembly of Janus cyclodextrins at the air-water interface and in organic solvents}, author = {B Hamelin and L Jullien and A Laschewsky and C Herv\'{e} Du Penhoat}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0033046267&doi=10.1002%2f%28SICI%291521-3765%2819990201%295%3a2%3c546%3a%3aAID-CHEM546%3e3.0.CO%3b2-I&partnerID=40&md5=1aa2c5f97b3dfcdef0f221c8c886e0dc}, doi = {10.1002/(SICI)1521-3765(19990201)5:2<546::AID-CHEM546>3.0.CO;2-I}, year = {1999}, date = {1999-01-01}, journal = {Chemistry - A European Journal}, volume = {5}, number = {2}, pages = {546--556}, abstract = {The self-organization of various amphiphilic cyclodextrins is reported at the air-water interface as well as in organic solvents. These rather rigid molecules expose different molecular surfaces to the external medium according to the nature of the environment, and consequently several types of association are observed. At the air-water interface, stable mono-and multilayers are formed whose behavior can be related to the molecular structure of the amphiphilic compounds. In apolar aromatic solvents, such as benzene or toluene, dimerization occurs as shown by vapour pressure osmometry (VPO), 1H NMR spectroscopy and 1H13C heteronuclear NOE measurements. Such a feature is absent in organic solvents that compete for the formation of hydrogen bonds. The consequences of these results concerning the use of cyclodextrin derivatives as calibration standards for the determination of molecular weights are discussed.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The self-organization of various amphiphilic cyclodextrins is reported at the air-water interface as well as in organic solvents. These rather rigid molecules expose different molecular surfaces to the external medium according to the nature of the environment, and consequently several types of association are observed. At the air-water interface, stable mono-and multilayers are formed whose behavior can be related to the molecular structure of the amphiphilic compounds. In apolar aromatic solvents, such as benzene or toluene, dimerization occurs as shown by vapour pressure osmometry (VPO), 1H NMR spectroscopy and 1H13C heteronuclear NOE measurements. Such a feature is absent in organic solvents that compete for the formation of hydrogen bonds. The consequences of these results concerning the use of cyclodextrin derivatives as calibration standards for the determination of molecular weights are discussed. |
Thermodynamic Behavior of a Supramolecular System Self-Assembled by Electrostatic Interaction in Aqueous Solution. Results and Theoretical Analysis Article de journal L Jullien; H Cottet; B Hamelin; A Jardy Journal of Physical Chemistry B, 103 (49), p. 10866–10875, 1999. @article{Jullien:1999, title = {Thermodynamic Behavior of a Supramolecular System Self-Assembled by Electrostatic Interaction in Aqueous Solution. Results and Theoretical Analysis}, author = {L Jullien and H Cottet and B Hamelin and A Jardy}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0001597844&partnerID=40&md5=ea841685fb09dc1a9df850eb4e6a2b9f}, year = {1999}, date = {1999-01-01}, journal = {Journal of Physical Chemistry B}, volume = {103}, number = {49}, pages = {10866--10875}, abstract = {The acid-base and association properties of oppositely charged cyclodextrins in aqueous solution have been investigated by potentiometry. The experimental thermodynamic constants can be analyzed with a theoretical approach leading to structural data in satisfactory agreement with the crystallographic structures of the parent compounds and previous NMR investigations. The corresponding theory is expected to be helpful for understanding and for predicting the behavior of many supramolecular systems involving charged organic molecules.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The acid-base and association properties of oppositely charged cyclodextrins in aqueous solution have been investigated by potentiometry. The experimental thermodynamic constants can be analyzed with a theoretical approach leading to structural data in satisfactory agreement with the crystallographic structures of the parent compounds and previous NMR investigations. The corresponding theory is expected to be helpful for understanding and for predicting the behavior of many supramolecular systems involving charged organic molecules. |
Towards highly efficient nonlinear optical chromophores: molecular engineering of octupolar molecules Article de journal M Blanchard-Desce; J -B Baudin; L Jullien; R Lome; O Ruel; S Brasselet; J Zyss 12 (2), p. 333–338, 1999. @article{Blanchard-Desce:1999, title = {Towards highly efficient nonlinear optical chromophores: molecular engineering of octupolar molecules}, author = {M Blanchard-Desce and J -B Baudin and L Jullien and R Lome and O Ruel and S Brasselet and J Zyss}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0032599630&doi=10.1016%2fS0925-3467%2899%2900059-2&partnerID=40&md5=608ca6fec7e1b491b2489ad8d402903e}, doi = {10.1016/S0925-3467(99)00059-2}, year = {1999}, date = {1999-01-01}, volume = {12}, number = {2}, pages = {333--338}, abstract = {Octupolar molecules are of particular interest in the field of nonlinear optics due to their potentially large two or three-dimensional quadratic nonlinearities. In order to design molecules combining enhanced first hyperpolarizabilities and excellent transparency, we have implemented an original strategy based upon adequate functionalization of an orthogonalized biphenyl core. We have designed novel 3-dimensional all-organic octupoles of D2d symmetry and investigated their optical nonlinearities by performing harmonic light scattering experiments in solution. By grafting four electron-donating and/or electron withdrawing substituents on the central biphenyl unit, large molecular nonlinearities (β) have been achieved while maintaining full transparency in the visible range. Molecules displaying larger nonlinearities and better transparency than pNA have been obtained. Molecular optimization has been further pursued via tethering elongated conjugated spikes on the central biphenyl core and taking advantage of multidimensional charge transfer leading to 3D-octupolar molecules displaying both larger nonlinearity and broader transparency than DR1 (up to βxyz = 145 × 10-30 esu with λmax = 400 nm).}, keywords = {}, pubstate = {published}, tppubtype = {article} } Octupolar molecules are of particular interest in the field of nonlinear optics due to their potentially large two or three-dimensional quadratic nonlinearities. In order to design molecules combining enhanced first hyperpolarizabilities and excellent transparency, we have implemented an original strategy based upon adequate functionalization of an orthogonalized biphenyl core. We have designed novel 3-dimensional all-organic octupoles of D2d symmetry and investigated their optical nonlinearities by performing harmonic light scattering experiments in solution. By grafting four electron-donating and/or electron withdrawing substituents on the central biphenyl unit, large molecular nonlinearities (β) have been achieved while maintaining full transparency in the visible range. Molecules displaying larger nonlinearities and better transparency than pNA have been obtained. Molecular optimization has been further pursued via tethering elongated conjugated spikes on the central biphenyl core and taking advantage of multidimensional charge transfer leading to 3D-octupolar molecules displaying both larger nonlinearity and broader transparency than DR1 (up to βxyz = 145 × 10-30 esu with λmax = 400 nm). |
1998 |
How does the gibbs free energy evolve in a system undergoing coupled competitive reactions? Article de journal L Jullien; A Proust; J -C Le Menn Journal of Chemical Education, 75 (2), p. 194–199, 1998. @article{Jullien:1998, title = {How does the gibbs free energy evolve in a system undergoing coupled competitive reactions?}, author = {L Jullien and A Proust and J -C Le Menn}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0039784723&partnerID=40&md5=9b76ac0d9cea46672dc9ee93fc16e5be}, year = {1998}, date = {1998-01-01}, journal = {Journal of Chemical Education}, volume = {75}, number = {2}, pages = {194--199}, keywords = {}, pubstate = {published}, tppubtype = {article} } |
Self-assembly of a molecular capsule driven by electrostatic interaction in aqueous solution Article de journal B Hamelin; L Jullien; C Derouet; C H Du Penhoat; P Berthault Journal of the American Chemical Society, 120 (33), p. 8438–8447, 1998. @article{Hamelin:1998, title = {Self-assembly of a molecular capsule driven by electrostatic interaction in aqueous solution}, author = {B Hamelin and L Jullien and C Derouet and C H Du Penhoat and P Berthault}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0032569193&doi=10.1021%2fja980046g&partnerID=40&md5=c9d806283a479743d90bfd37476a326d}, doi = {10.1021/ja980046g}, year = {1998}, date = {1998-01-01}, journal = {Journal of the American Chemical Society}, volume = {120}, number = {33}, pages = {8438--8447}, abstract = {A self-assembling molecular capsule based on electrostatic interaction has been designed and its structure is investigated by dynamic 1H NMR. The hydrodynamic description resulting from relaxation and PGSE 1H NMR experiments indicates that association between oppositely charged hydrophilic β-cyclodextrin derivatives in 50 mM KCl aqueous solution corresponds to dimerization with an interdistance between interacting units lying in the 0.4-1.1 nm range with a maximal probability at 0.6 nm.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A self-assembling molecular capsule based on electrostatic interaction has been designed and its structure is investigated by dynamic 1H NMR. The hydrodynamic description resulting from relaxation and PGSE 1H NMR experiments indicates that association between oppositely charged hydrophilic β-cyclodextrin derivatives in 50 mM KCl aqueous solution corresponds to dimerization with an interdistance between interacting units lying in the 0.4-1.1 nm range with a maximal probability at 0.6 nm. |
1997 |
Does aggregation modulate the apparent association constant of host-guest complexes and related species? Article de journal B Hamelin; L Jullien Journal of the Chemical Society - Faraday Transactions, 93 (12), p. 2153–2160, 1997. @article{Hamelin:1997, title = {Does aggregation modulate the apparent association constant of host-guest complexes and related species?}, author = {B Hamelin and L Jullien}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-33748597387&doi=10.1039%2fa700730b&partnerID=40&md5=d8bad9212598488e98e6367d09cd6f83}, doi = {10.1039/a700730b}, year = {1997}, date = {1997-01-01}, journal = {Journal of the Chemical Society - Faraday Transactions}, volume = {93}, number = {12}, pages = {2153--2160}, abstract = {The present paper illustrates the consequences of aggregation phenomena on the apparent association constant of a host-guest system in three different cases. In the first, the guest gives aggregates whereas in the second the host exhibits aggregation while maintaining a constant affinity for the guest. In the last case under examination, it is the host-guest species that is assumed to aggregate. Numerical simulations based on widely used experimental protocols emphasized the significance of aggregation phenomena on apparent association constants under a broad range of circumstances. The possible relevance of the present analysis to real systems is discussed.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The present paper illustrates the consequences of aggregation phenomena on the apparent association constant of a host-guest system in three different cases. In the first, the guest gives aggregates whereas in the second the host exhibits aggregation while maintaining a constant affinity for the guest. In the last case under examination, it is the host-guest species that is assumed to aggregate. Numerical simulations based on widely used experimental protocols emphasized the significance of aggregation phenomena on apparent association constants under a broad range of circumstances. The possible relevance of the present analysis to real systems is discussed. |
Dynamic behavior of a perfunctionalized β-cyclodextrin as probed by NMR and molecular modeling Article de journal L Catoire; V Michon; L Monville; A Hocquet; L Jullien; J Canceill; J -M Lehn; M Piotto; C H Du Penhoat Carbohydrate Research, 303 (4), p. 379–393, 1997. @article{Catoire:1997a, title = {Dynamic behavior of a perfunctionalized β-cyclodextrin as probed by NMR and molecular modeling}, author = {L Catoire and V Michon and L Monville and A Hocquet and L Jullien and J Canceill and J -M Lehn and M Piotto and C H Du Penhoat}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0030730720&doi=10.1016%2fS0008-6215%2897%2900188-2&partnerID=40&md5=5a1d95947c311db10fcad166684adcfe}, doi = {10.1016/S0008-6215(97)00188-2}, year = {1997}, date = {1997-01-01}, journal = {Carbohydrate Research}, volume = {303}, number = {4}, pages = {379--393}, abstract = {Conformational analysis of a perfunctionalized β-cyclodextrin by NMR and molecular modeling has revealed that this compound exists as an equilibrium mixture of C1 and C7 conformers in slow exchange. From carbon chemical shifts, interglycosidic vicinal heteronuclear coupling constants and NOESY volumes, it has been demonstrated that the macrocyclic conformation is responsable for the asymmetry in the C1 form. Several dynamic processes such as rapid conformational averaging, localized chemical exchange and the C1/C7 equilibrium have been shown to occur on widely separated timescales. In parallel, a molecular modeling study has revealed that the accessible conformational space of β-CDs is not significantly reduced with respect to that of the related disaccharide, β-maltose. All of the dynamic phenomena appear to be related to the macrocylic puckering and two distinct modes of variation in puckering have emerged from MD trajectories: transitions are either auto-compensated without perceptible change in macrocycle puckering or irreversible leading to considerable variation in macrocycle puckering. Optimization of the NMR-defined theoretical structures leads to auto- complexation of an exocyclic substituent.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Conformational analysis of a perfunctionalized β-cyclodextrin by NMR and molecular modeling has revealed that this compound exists as an equilibrium mixture of C1 and C7 conformers in slow exchange. From carbon chemical shifts, interglycosidic vicinal heteronuclear coupling constants and NOESY volumes, it has been demonstrated that the macrocyclic conformation is responsable for the asymmetry in the C1 form. Several dynamic processes such as rapid conformational averaging, localized chemical exchange and the C1/C7 equilibrium have been shown to occur on widely separated timescales. In parallel, a molecular modeling study has revealed that the accessible conformational space of β-CDs is not significantly reduced with respect to that of the related disaccharide, β-maltose. All of the dynamic phenomena appear to be related to the macrocylic puckering and two distinct modes of variation in puckering have emerged from MD trajectories: transitions are either auto-compensated without perceptible change in macrocycle puckering or irreversible leading to considerable variation in macrocycle puckering. Optimization of the NMR-defined theoretical structures leads to auto- complexation of an exocyclic substituent. |
pH-dependent specific binding and combing of DNA Article de journal J -F Allemand; D Bensimon; L Jullien; A Bensimon; V Croquette Biophysical Journal, 73 (4), p. 2064–2070, 1997. @article{Allemand:1997, title = {pH-dependent specific binding and combing of DNA}, author = {J -F Allemand and D Bensimon and L Jullien and A Bensimon and V Croquette}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0030881494&doi=10.1016%2fS0006-3495%2897%2978236-5&partnerID=40&md5=67fabb87ba140361b6bc5c28e2ea523a}, doi = {10.1016/S0006-3495(97)78236-5}, year = {1997}, date = {1997-01-01}, journal = {Biophysical Journal}, volume = {73}, number = {4}, pages = {2064--2070}, abstract = {Recent developments in the rapid sequencing, mapping, and analysis of DNA rely on the specific binding of DNA to specially treated surfaces. We show here that specific binding of DNA via its unmodified extremities can be achieved on a great variety of surfaces by a judicious choice of the pH. On hydrophobic surfaces the best binding efficiency is reached at a pH of textasciitilde5.5. At that pH textasciitilde40-kbp DNA is 10 times more likely to bind by an extremity than by a midsegment. A model is proposed to account for the differential adsorption of the molecule extremities and midsection as a function of pH. The pH-dependent specific binding can be used to align anchored DNA molecules by a receding meniscus, a process called molecular combing. The resulting properties of the combed molecules will be discussed.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Recent developments in the rapid sequencing, mapping, and analysis of DNA rely on the specific binding of DNA to specially treated surfaces. We show here that specific binding of DNA via its unmodified extremities can be achieved on a great variety of surfaces by a judicious choice of the pH. On hydrophobic surfaces the best binding efficiency is reached at a pH of textasciitilde5.5. At that pH textasciitilde40-kbp DNA is 10 times more likely to bind by an extremity than by a midsegment. A model is proposed to account for the differential adsorption of the molecule extremities and midsection as a function of pH. The pH-dependent specific binding can be used to align anchored DNA molecules by a receding meniscus, a process called molecular combing. The resulting properties of the combed molecules will be discussed. |
1996 |
Interaction, lipid exchange, and effect of vesicle size in systems of oppositely charged vesicles Article de journal V Marchi-Artzner; L Jullien; L Belloni; D Raison; L Lacombe; J -M Lehn Journal of Physical Chemistry, 100 (32), p. 13844–13856, 1996. @article{Marchi-Artzner:1996, title = {Interaction, lipid exchange, and effect of vesicle size in systems of oppositely charged vesicles}, author = {V Marchi-Artzner and L Jullien and L Belloni and D Raison and L Lacombe and J -M Lehn}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0000460872&doi=10.1021%2fjp960327f&partnerID=40&md5=3795a27b061ada113fcc14c7fe016f95}, doi = {10.1021/jp960327f}, year = {1996}, date = {1996-01-01}, journal = {Journal of Physical Chemistry}, volume = {100}, number = {32}, pages = {13844--13856}, abstract = {The interactions between charged unilamellar vesicles of different size prepared from mixtures of egg lecithin (EPC1), cholesterol, and a charged component, either stearylamine or dicetyl phosphate, were investigated. Several techniques, i.e. fluorescence spectroscopy, 133Cs-NMR, light scattering measurements, and electron and optical microscopies in dilute aqueous solutions, provided evidence that vesicles bearing opposite charges interact via contact followed by lipid exchange; the progressive charge neutralization is shown by 133Cs-NMR to occur without fusion of vesicle internal pools. Vesicle size determines as diverse features as contact duration, extent of lipid exchange, and final distribution of surface charge among the vesicle mixture. © 1996 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The interactions between charged unilamellar vesicles of different size prepared from mixtures of egg lecithin (EPC1), cholesterol, and a charged component, either stearylamine or dicetyl phosphate, were investigated. Several techniques, i.e. fluorescence spectroscopy, 133Cs-NMR, light scattering measurements, and electron and optical microscopies in dilute aqueous solutions, provided evidence that vesicles bearing opposite charges interact via contact followed by lipid exchange; the progressive charge neutralization is shown by 133Cs-NMR to occur without fusion of vesicle internal pools. Vesicle size determines as diverse features as contact duration, extent of lipid exchange, and final distribution of surface charge among the vesicle mixture. © 1996 American Chemical Society. |
Multichromophoric cyclodextrins. 3. Investigation of dynamics of energy hopping by frequency-domain fluorometry Article de journal M N Berberan-Santos; J Canceill; E Gratton; L Jullien; J -M Lehn; P So; J Sutin; B Valeur Journal of Physical Chemistry, 100 (1), p. 15–20, 1996. @article{Berberan-Santos:1996, title = {Multichromophoric cyclodextrins. 3. Investigation of dynamics of energy hopping by frequency-domain fluorometry}, author = {M N Berberan-Santos and J Canceill and E Gratton and L Jullien and J -M Lehn and P So and J Sutin and B Valeur}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0003019274&doi=10.1021%2fjp951598d&partnerID=40&md5=99ebe5d1e0d18c77b7580fe2784de54a}, doi = {10.1021/jp951598d}, year = {1996}, date = {1996-01-01}, journal = {Journal of Physical Chemistry}, volume = {100}, number = {1}, pages = {15--20}, abstract = {A β-cyclodextrin labeled with seven naphthoyloxy chromophores was studied by steady-state and time-resolved fluorescence spectroscopy in order to get information on the dynamics of energy hopping between chromophores. The steady-state fluorescence anisotropy was recorded as a function of excitation wavelength in a mixture of methanol and ethanol at 110 K (rigid glass). The fluorescence anisotropy decay was obtained under the same conditions by the multifrequency phase-modulation technique upon excitation at 290 nm. The data were analyzed and interpreted on the basis of a theoretical model involving a unique rate constant for energy hopping between nearest neighbors. In particular, this model predicts a long-time leveling-off of the emission anisotropy at 1/7th of the fundamental anisotropy, which is confirmed by both steady-state and time-resolved data and thus indicates that there is no preferred mutual orientation between the chromophores. As regards the rate of energy hopping, an average value of 2 × 109 s-1 can be deduced from the comparison between the theoretical and experimental decays. This value is shown to be consistent with a dipole-dipole mechanism of energy transfer. © 1996 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A β-cyclodextrin labeled with seven naphthoyloxy chromophores was studied by steady-state and time-resolved fluorescence spectroscopy in order to get information on the dynamics of energy hopping between chromophores. The steady-state fluorescence anisotropy was recorded as a function of excitation wavelength in a mixture of methanol and ethanol at 110 K (rigid glass). The fluorescence anisotropy decay was obtained under the same conditions by the multifrequency phase-modulation technique upon excitation at 290 nm. The data were analyzed and interpreted on the basis of a theoretical model involving a unique rate constant for energy hopping between nearest neighbors. In particular, this model predicts a long-time leveling-off of the emission anisotropy at 1/7th of the fundamental anisotropy, which is confirmed by both steady-state and time-resolved data and thus indicates that there is no preferred mutual orientation between the chromophores. As regards the rate of energy hopping, an average value of 2 × 109 s-1 can be deduced from the comparison between the theoretical and experimental decays. This value is shown to be consistent with a dipole-dipole mechanism of energy transfer. © 1996 American Chemical Society. |
Multichromophoric cyclodextrins. 4. Light conversion by antenna effect Article de journal L Jullien; J Canceill; B Valeur; E Bardez; J -P Lefèvre; J -M Lehn; V Marchi-Artzner; R Pansu Journal of the American Chemical Society, 118 (23), p. 5432–5442, 1996. @article{Jullien:1996, title = {Multichromophoric cyclodextrins. 4. Light conversion by antenna effect}, author = {L Jullien and J Canceill and B Valeur and E Bardez and J -P Lef\`{e}vre and J -M Lehn and V Marchi-Artzner and R Pansu}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0029953291&doi=10.1021%2fja954332t&partnerID=40&md5=86be6c0094475ed11e09091268977ba1}, doi = {10.1021/ja954332t}, year = {1996}, date = {1996-01-01}, journal = {Journal of the American Chemical Society}, volume = {118}, number = {23}, pages = {5432--5442}, abstract = {A water soluble β-cyclodextrin (CD-NA) bearing seven naphthoyl chromophores forms very stable 1:1 complexes with a merocyanine laser dye DCM-OH (4-(dicyanomethylene)-2-methyl-6-(p-(bis(hydroxyethyl)amino)-styryl)-4 H-pyran). The antenna effect, i.e. energy transfer from the naphthoyl antenna chromophores to the encased dye, is shown to occur with 100% efficiency. The stability of the complexes is very high (K(s) textasciitilde 105) owing to the contribution of the naphthoate residues. The structural features of the complexes have been examined in detail: circular dichroism experiments confirm the expected axial orientation of DCM-OH in the cavity of CD-NA, and fluorescence anisotropy measurements together with 13C-NMR longitudinal relaxation time measurements show that the complex formed between CD-NA and DCM-OH is tight. The mechanisms of homotransfer (i.e., between naphthoate chromophores) and heterotransfer (i.e., from naphthoate chromophores to DCM-OH included in the cavity) are discussed in light of existing theories. In both cases, the major contribution arises more likely from Coulombic interaction than from short-range interactions. Such multichromophoric cyclodextrins are good models for mimicry of the antenna function in photosynthesis and show great promise as photochemical microreactors.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A water soluble β-cyclodextrin (CD-NA) bearing seven naphthoyl chromophores forms very stable 1:1 complexes with a merocyanine laser dye DCM-OH (4-(dicyanomethylene)-2-methyl-6-(p-(bis(hydroxyethyl)amino)-styryl)-4 H-pyran). The antenna effect, i.e. energy transfer from the naphthoyl antenna chromophores to the encased dye, is shown to occur with 100% efficiency. The stability of the complexes is very high (K(s) textasciitilde 105) owing to the contribution of the naphthoate residues. The structural features of the complexes have been examined in detail: circular dichroism experiments confirm the expected axial orientation of DCM-OH in the cavity of CD-NA, and fluorescence anisotropy measurements together with 13C-NMR longitudinal relaxation time measurements show that the complex formed between CD-NA and DCM-OH is tight. The mechanisms of homotransfer (i.e., between naphthoate chromophores) and heterotransfer (i.e., from naphthoate chromophores to DCM-OH included in the cavity) are discussed in light of existing theories. In both cases, the major contribution arises more likely from Coulombic interaction than from short-range interactions. Such multichromophoric cyclodextrins are good models for mimicry of the antenna function in photosynthesis and show great promise as photochemical microreactors. |
1995 |
Drug delivery: Piercing vesicles by their adsorption onto a porous medium Article de journal M -A Guedeau-Boudeville; L Jullien; J -M Di Meglio Proceedings of the National Academy of Sciences of the United States of America, 92 (21), p. 9590–9592, 1995. @article{Guedeau-Boudeville:1995, title = {Drug delivery: Piercing vesicles by their adsorption onto a porous medium}, author = {M -A Guedeau-Boudeville and L Jullien and J -M Di Meglio}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0028820145&doi=10.1073%2fpnas.92.21.9590&partnerID=40&md5=251b948d8859e06857263108f1f5e581}, doi = {10.1073/pnas.92.21.9590}, year = {1995}, date = {1995-01-01}, journal = {Proceedings of the National Academy of Sciences of the United States of America}, volume = {92}, number = {21}, pages = {9590--9592}, abstract = {Experimental evidence is presented that supports the possibility of building a 'molecular drill.' By the adsorption of a vesicle onto a porous substrate (specifically, a lycopode grain), it was possible to increase the permeability of the vesicle by locally stretching its membrane. Molecules contained within the vesicle, which could not cross the membrane, were delivered to the porous substrate upon adsorption. This general process could provide another method for drug delivery and targeting.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Experimental evidence is presented that supports the possibility of building a 'molecular drill.' By the adsorption of a vesicle onto a porous substrate (specifically, a lycopode grain), it was possible to increase the permeability of the vesicle by locally stretching its membrane. Molecules contained within the vesicle, which could not cross the membrane, were delivered to the porous substrate upon adsorption. This general process could provide another method for drug delivery and targeting. |
Formation of highly stable heterodimers in aqueous solution between β-cyclodextrin derivatives bearing multiple opposite charges Article de journal B Hamelin; L Jullien; F Guillo; J -M Lehn; A Jardy; L De Robertis; H Driguez Journal of Physical Chemistry, 99 (51), p. 17877–17885, 1995. @article{Hamelin:1995, title = {Formation of highly stable heterodimers in aqueous solution between β-cyclodextrin derivatives bearing multiple opposite charges}, author = {B Hamelin and L Jullien and F Guillo and J -M Lehn and A Jardy and L De Robertis and H Driguez}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-0000285072&partnerID=40&md5=34255c509ef04ce2b93b4a7f1cf9684a}, year = {1995}, date = {1995-01-01}, journal = {Journal of Physical Chemistry}, volume = {99}, number = {51}, pages = {17877--17885}, abstract = {Two water-soluble perfunctionalized β-cyclodextrins bearing amino or carboxyl groups were used to examine the possibility of obtaining stable heterodimers in water. The acidobasic properties of both compounds may be accounted for on the basis of a theoretical interpretation of the potentiometric titration of polyelectrolytes. The association constants between positively and negatively charged β-cyclodextrins were determined by potentiometric titrations. The Gibbs energies of association between cyclodextrins are shown to depend on the product of elementary charges borne by each interacting species. The results obtained are significant for evaluation of electrostatic contributions to molecular recognition. © 1995 American Chemical Society.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Two water-soluble perfunctionalized β-cyclodextrins bearing amino or carboxyl groups were used to examine the possibility of obtaining stable heterodimers in water. The acidobasic properties of both compounds may be accounted for on the basis of a theoretical interpretation of the potentiometric titration of polyelectrolytes. The association constants between positively and negatively charged β-cyclodextrins were determined by potentiometric titrations. The Gibbs energies of association between cyclodextrins are shown to depend on the product of elementary charges borne by each interacting species. The results obtained are significant for evaluation of electrostatic contributions to molecular recognition. © 1995 American Chemical Society. |