Cyrille Monnereau - Academia.edu (original) (raw)
Papers by Cyrille Monnereau
Recent examples of our works in the field of molecular engineering of chromophores for two-photon... more Recent examples of our works in the field of molecular engineering of chromophores for two-photon photodynamic therapy (PDT), and their vectorization into biological medium are presented and discussed. In a first section of this article, we show that a commercial amphiphilic diblock copolymer can be used as a micellar container for efficient delivery of s standard two-photon PDT sensitizer into
In the present article, we review several of the most significant recent advancements in the fiel... more In the present article, we review several of the most significant recent advancements in the field of specific chromophore engineering for nonlinear biophotonics. We focus more particularly on four different class of applications: probes for nonlinear microscopy imaging of cell cultures, probes responsive to a chemical stimulus, probes undergoing nonlinear photoinduced processes in the cell, and probes for nonlinear fluorescence imaging in vivo.
Optics and Photonics for Counterterrorism, Crime Fighting, and Defence X; and Optical Materials and Biomaterials in Security and Defence Systems Technology XI, 2014
This article provides an overview of the photophysical behavior diversity of polymethine chromoph... more This article provides an overview of the photophysical behavior diversity of polymethine chromophores which are ubiquitous in biological imaging and material sciences. One major challenge in this class of chromophore is to correlate the chemical structure to the observed optical properties, especially when symmetry-breaking phenomena occur. With the constant concern for rationalization of their spectroscopy, we propose an extended classification of polymethine dyes based on their ground state electronic configuration using three limit forms namely: cyanine, dipole and bis-dipole. The chemical modifications of the dye and the influence of exogenous parameters can promote dramatic spectroscopic changes that can be correlated to significant electronic reorganization between the three-abovementioned forms. The deep understanding of such phenomena should allow to identify, predict and take advantage of the versatile electronic structure of polymethines.
Organic Optoelectronics and Photonics II, 2006
Several polymer molecules have structures which are suitable for the non-linear optic application... more Several polymer molecules have structures which are suitable for the non-linear optic applications. We report on the design and fabrication of a high performance electro-optic modulator made of polymer thin films. The polymer we study contains a chromophore based on Disperse Red One covalently grafted to a host-matrix. The polymer materials are deposited in thin layers on a glass substrate
The journal of physical chemistry. A, Jan 12, 2014
Although it has been reported in a few instances that the spectroscopic properties of cyanine dye... more Although it has been reported in a few instances that the spectroscopic properties of cyanine dyes were strongly dependent on the nature of the chemical substitution of their central carbon atom, there has not been to date any systematic study specifically aimed at rationalizing this behavior. In this article, such a systematic study is carried out on an extended family of 17 polymethine dyes carrying different substituents on their central carbon, some of those being specifically synthesized for this study, some of those similar to previously reported compounds, for the sake of comparison. Their absorption properties, which spread over the whole visible to near-infrared spectral range, are seen to be dramatically dependent on the electron-donating character of this central substituent. By correlating this behavior to NMR spectroscopy and (vibronic) TD-DFT calculations, we show that it results from a profound modification of the ground state electronic configuration, namely, a progr...
Tetrahedron Letters, 2005
ABSTRACT
Journal de Chimie Physique et de Physico-Chimie Biologique, 1999
The feasibility of experiments on the physics of foams in microgravity environment was investigat... more The feasibility of experiments on the physics of foams in microgravity environment was investigated during a parabolic flight campaign. Transient foams from surfactant-free organic liquids and stable foams from a soapy solution of a Sodium Dodecyl Sulfate + Dodecanol mixture were investigated. In 0g, the transient foam is stabilized; whatever the liquid the foam bubbles are spherical and their diameter
Optical Materials and Biomaterials in Security and Defence Systems Technology IX, 2012
ABSTRACT We have recently initiated a research project that aims at understanding how systematic ... more ABSTRACT We have recently initiated a research project that aims at understanding how systematic variations of the number and positioning of a given Inter-System Crossing (ISC) promoter (1,4-dibromophenyl) along the Intramolecular Charge Transfer (ICT) axis of chromophores will affect the outcome of singlet oxygen production, and how this effect will be related to the nature of the ICT transition. In this communication, this strategy is discussed and we show that a clear influence of the ISC promoter’s position on the chromophore exists, which can be used both to improve the singlet oxygen generation efficiency of the sensitizer, but also its linear and nonlinear spectroscopic features.
Proceedings of SPIE - The International Society for Optical Engineering, 2002
Recent examples of our works in the field of molecular engineering of chromophores for two-photon... more Recent examples of our works in the field of molecular engineering of chromophores for two-photon photodynamic therapy (PDT), and their vectorization into biological medium are presented and discussed. In a first section of this article, we show that a commercial amphiphilic diblock copolymer can be used as a micellar container for efficient delivery of s standard two-photon PDT sensitizer into
The Journal of Physical Chemistry A, 2010
A series of Zn(II) porphyrin (ZnP) compounds covalently linked to different electron acceptor uni... more A series of Zn(II) porphyrin (ZnP) compounds covalently linked to different electron acceptor units, naphthaleneimide (NI) and naphthalenediimide (NDI), are reported. The aim was to demonstrate a state-selective direction of electron transfer, where excitation to the lowest excited S(1) state of the porphyrin (Q-band excitation) would give electron transfer to the NDI unit, while excitation to the higher S(2) state (Soret-band excitation) would give electron transfer to the NI unit. This would constitute a basis for an opto-electronic switch in which the direction of electron transfer and the resulting dipole moment can be controlled by using light input of different color. Indeed, electron transfer from the S(1) state to NDI occurred in solvents of both high and low polarity, whereas no electron transfer to NDI was observed from the S(2) state. With NI as acceptor instead, very rapid (tau = 200-400 fs) electron transfer from the S(2) state occurred in all solvents. This was followed by an ultrafast (tau approximately 100 fs) recombination to populate the porphyrin S(1) state in nearly quantitative yield. The charge-separated state ZnP(+)NI(-) was spectroscopically observed, and evidence was obtained that recombination occurred from a vibrationally excited ("hot") ZnP(+)NI(-) state in the more polar solvents. In these solvents, the thermally relaxed ZnP(+)NI(-) state lies at lower energy than the S(1) state so that further charge separation occurred from S(1) to form ZnP(+)NI(-). This resulted in a highly unusual "ping-pong" sequence where the reaction went back and forth between locally excited ZnP states and charge-separated states: S(2) --> ZnP(+)NI(-)("hot") --> S(1) --> ZnP(+)NI(-) --> S(0). The electron transfer dynamics and its solvent dependence are discussed, as well as the function of the present molecules as molecular switches.
Tetrahedron, 2005
In this paper, the synthesis of a crosslinkable co-polymer containing new pushpull arylethynyl z... more In this paper, the synthesis of a crosslinkable co-polymer containing new pushpull arylethynyl zinc porphyrins is described. The synthesis of porphyrin chromophores, analogous to Therien's porphyrin (J. Am. Chem. Soc. 1996, 118, 14971503) ...
Science, 2008
The translocation of biopolymers through pores and channels plays a fundamental role in numerous ... more The translocation of biopolymers through pores and channels plays a fundamental role in numerous biological processes. We describe here the mechanism of the threading of a series of polymer chains through a synthetic macrocycle, which mimics these natural processes. The threading of polymers involves a kinetically favorable "entron" effect, which is associated with the initial filling of the cavity by the end of the polymer. A preassociation between the outside of the macrocycle and the polymer induces a process in which the polymer end loops back into the cavity of the macrocycle. This looping mechanism results in accelerated threading rates and unidirectional motion and is reminiscent of the protein translocation through membrane pores.
![Research paper thumbnail of Self-assembly of dimeric tetraurea calix[4]pyrrole capsules](https://attachments.academia-assets.com/41442412/thumbnails/1.jpg)
](Proceedings of the National Academy of Sciences, 2009
Calix[4]pyrroles having extended aromatic cavities have been functionalized with 4 ureas in the p... more Calix[4]pyrroles having extended aromatic cavities have been functionalized with 4 ureas in the para position of their meso phenyl substituents. This elaboration of the upper rim was completed in 2 synthetic steps starting from the ␣,␣,␣,␣-tetranitro isomer of the calix[4]pyrrole obtained in the acid catalyzed condensation of p-nitrophenyl methyl ketone and pyrrole. In dichloromethane solution and in the presence of 4,4-bipyridine N-N-dioxide the tetraurea calix[4]pyrrole dimerizes reversibly forming a cyclic array of 16 hydrogen bonds and encapsulating 1 molecule of bis-N-oxide. The encapsulated guest is bound in the cavity by hydrogen bonding to the 2 endohedral calix[4]pyrrole centers. Further evidence for dimerization of the tetraurea calix[4]pyrroles is provided by 1 H-NMR experiments and by the formation of mixed capsules.
Polymer Chemistry, 2012
An original and mild bromination protocol allows a poly-(hydroxyethyl acrylate) polymer synthesiz... more An original and mild bromination protocol allows a poly-(hydroxyethyl acrylate) polymer synthesized by ATRP to be converted readily and quantitatively into its corresponding poly-(bromoethyl acrylate) analogue. We show that the latter can be used as a common precursor towards ionic-liquid containing polymers.
Organic & Biomolecular Chemistry, 2012
A molecular engineering strategy based on rational variations of the bromine substitution pattern... more A molecular engineering strategy based on rational variations of the bromine substitution pattern in two-photon absorbing singlet oxygen sensitizers allows studying the relations that exist between the positioning of an inter-system crossing promoter on the charge-transfer chromophore and its ability to generate singlet oxygen.
New Journal of Chemistry, 2012
A simple polymerisation strategy allows water solubilisation of chromophores for biophotonics, wi... more A simple polymerisation strategy allows water solubilisation of chromophores for biophotonics, with good conservation of their fluorescence quantum-yield. Preliminary investigations show that the resulting objects are valuable candidates for photodynamic therapy and two-photon fluorescence imaging.
Journal of the American Chemical Society, 2010
Natural proteins and enzymes have been widely used as blueprints for the construction of syntheti... more Natural proteins and enzymes have been widely used as blueprints for the construction of synthetic catalysts. 1 As mimics for the monooxygenase cytochrome P450, myriads of modifications have been introduced into the skeleton of catalytic porphyrins with the purpose to improve the degree of control over the catalytic reactions and to reach efficiencies comparable to that of natural enzymes. 2 For example, nitrogen containing axial ligands have been used to enhance the rate of oxidation catalysts by activating the manganese-oxygen bond of Mn(III) porphyrins; 3 electron donating or withdrawing groups of different nature have been added to the meso positions of these porphyrins to tune the electronic properties; i.e. the reactivity of the catalytic center; 4 and shape-selective or chiral binding pockets have been introduced to improve the chemoand stereoselectivities of the reaction. 5 Furthermore, bulky substituents have been attached to the porphyrin to provide spatial shielding, thus preventing deactivation of the catalyst by dimerization reactions. We have previously reported on the synthesis and study of a diphenylglycoluril-appended porphyrin catalyst Mn2 . Because of its open ring structure, this compound is capable of binding to a polymer chain, e.g. polybutadiene, and thread on it. 8 Kinetic studies have revealed that the catalyst can convert the double bonds of polybutadiene into epoxide functions while gliding along the polymer chain in a pseudorotaxane fashion 9 ). Because of this unique feature, this catalyst can be called a processive enzyme mimic. 10 In spite of the very promising results in terms of guest complexation, motion along the polymer chain, and oxidation of polymer substrates, the system has some drawbacks hampering its practical use as a processive catalyst. For instance, a large excess of a bulky coordinating ligand (a pyridine derivative) is required to efficiently shield the outer face of the catalyst, thereby facilitating the catalytic reaction to take place on the inside through a rotaxane mechanism. However, even at high concentrations of axial ligand, the outer face of the catalyst remained partially accessible, and as a result deactivation of the catalyst, probably by a dimerization reaction, still occurred. This led to premature stalling of the epoxidation process.
Recent examples of our works in the field of molecular engineering of chromophores for two-photon... more Recent examples of our works in the field of molecular engineering of chromophores for two-photon photodynamic therapy (PDT), and their vectorization into biological medium are presented and discussed. In a first section of this article, we show that a commercial amphiphilic diblock copolymer can be used as a micellar container for efficient delivery of s standard two-photon PDT sensitizer into
In the present article, we review several of the most significant recent advancements in the fiel... more In the present article, we review several of the most significant recent advancements in the field of specific chromophore engineering for nonlinear biophotonics. We focus more particularly on four different class of applications: probes for nonlinear microscopy imaging of cell cultures, probes responsive to a chemical stimulus, probes undergoing nonlinear photoinduced processes in the cell, and probes for nonlinear fluorescence imaging in vivo.
Optics and Photonics for Counterterrorism, Crime Fighting, and Defence X; and Optical Materials and Biomaterials in Security and Defence Systems Technology XI, 2014
This article provides an overview of the photophysical behavior diversity of polymethine chromoph... more This article provides an overview of the photophysical behavior diversity of polymethine chromophores which are ubiquitous in biological imaging and material sciences. One major challenge in this class of chromophore is to correlate the chemical structure to the observed optical properties, especially when symmetry-breaking phenomena occur. With the constant concern for rationalization of their spectroscopy, we propose an extended classification of polymethine dyes based on their ground state electronic configuration using three limit forms namely: cyanine, dipole and bis-dipole. The chemical modifications of the dye and the influence of exogenous parameters can promote dramatic spectroscopic changes that can be correlated to significant electronic reorganization between the three-abovementioned forms. The deep understanding of such phenomena should allow to identify, predict and take advantage of the versatile electronic structure of polymethines.
Organic Optoelectronics and Photonics II, 2006
Several polymer molecules have structures which are suitable for the non-linear optic application... more Several polymer molecules have structures which are suitable for the non-linear optic applications. We report on the design and fabrication of a high performance electro-optic modulator made of polymer thin films. The polymer we study contains a chromophore based on Disperse Red One covalently grafted to a host-matrix. The polymer materials are deposited in thin layers on a glass substrate
The journal of physical chemistry. A, Jan 12, 2014
Although it has been reported in a few instances that the spectroscopic properties of cyanine dye... more Although it has been reported in a few instances that the spectroscopic properties of cyanine dyes were strongly dependent on the nature of the chemical substitution of their central carbon atom, there has not been to date any systematic study specifically aimed at rationalizing this behavior. In this article, such a systematic study is carried out on an extended family of 17 polymethine dyes carrying different substituents on their central carbon, some of those being specifically synthesized for this study, some of those similar to previously reported compounds, for the sake of comparison. Their absorption properties, which spread over the whole visible to near-infrared spectral range, are seen to be dramatically dependent on the electron-donating character of this central substituent. By correlating this behavior to NMR spectroscopy and (vibronic) TD-DFT calculations, we show that it results from a profound modification of the ground state electronic configuration, namely, a progr...
Tetrahedron Letters, 2005
ABSTRACT
Journal de Chimie Physique et de Physico-Chimie Biologique, 1999
The feasibility of experiments on the physics of foams in microgravity environment was investigat... more The feasibility of experiments on the physics of foams in microgravity environment was investigated during a parabolic flight campaign. Transient foams from surfactant-free organic liquids and stable foams from a soapy solution of a Sodium Dodecyl Sulfate + Dodecanol mixture were investigated. In 0g, the transient foam is stabilized; whatever the liquid the foam bubbles are spherical and their diameter
Optical Materials and Biomaterials in Security and Defence Systems Technology IX, 2012
ABSTRACT We have recently initiated a research project that aims at understanding how systematic ... more ABSTRACT We have recently initiated a research project that aims at understanding how systematic variations of the number and positioning of a given Inter-System Crossing (ISC) promoter (1,4-dibromophenyl) along the Intramolecular Charge Transfer (ICT) axis of chromophores will affect the outcome of singlet oxygen production, and how this effect will be related to the nature of the ICT transition. In this communication, this strategy is discussed and we show that a clear influence of the ISC promoter’s position on the chromophore exists, which can be used both to improve the singlet oxygen generation efficiency of the sensitizer, but also its linear and nonlinear spectroscopic features.
Proceedings of SPIE - The International Society for Optical Engineering, 2002
Recent examples of our works in the field of molecular engineering of chromophores for two-photon... more Recent examples of our works in the field of molecular engineering of chromophores for two-photon photodynamic therapy (PDT), and their vectorization into biological medium are presented and discussed. In a first section of this article, we show that a commercial amphiphilic diblock copolymer can be used as a micellar container for efficient delivery of s standard two-photon PDT sensitizer into
The Journal of Physical Chemistry A, 2010
A series of Zn(II) porphyrin (ZnP) compounds covalently linked to different electron acceptor uni... more A series of Zn(II) porphyrin (ZnP) compounds covalently linked to different electron acceptor units, naphthaleneimide (NI) and naphthalenediimide (NDI), are reported. The aim was to demonstrate a state-selective direction of electron transfer, where excitation to the lowest excited S(1) state of the porphyrin (Q-band excitation) would give electron transfer to the NDI unit, while excitation to the higher S(2) state (Soret-band excitation) would give electron transfer to the NI unit. This would constitute a basis for an opto-electronic switch in which the direction of electron transfer and the resulting dipole moment can be controlled by using light input of different color. Indeed, electron transfer from the S(1) state to NDI occurred in solvents of both high and low polarity, whereas no electron transfer to NDI was observed from the S(2) state. With NI as acceptor instead, very rapid (tau = 200-400 fs) electron transfer from the S(2) state occurred in all solvents. This was followed by an ultrafast (tau approximately 100 fs) recombination to populate the porphyrin S(1) state in nearly quantitative yield. The charge-separated state ZnP(+)NI(-) was spectroscopically observed, and evidence was obtained that recombination occurred from a vibrationally excited ("hot") ZnP(+)NI(-) state in the more polar solvents. In these solvents, the thermally relaxed ZnP(+)NI(-) state lies at lower energy than the S(1) state so that further charge separation occurred from S(1) to form ZnP(+)NI(-). This resulted in a highly unusual "ping-pong" sequence where the reaction went back and forth between locally excited ZnP states and charge-separated states: S(2) --> ZnP(+)NI(-)("hot") --> S(1) --> ZnP(+)NI(-) --> S(0). The electron transfer dynamics and its solvent dependence are discussed, as well as the function of the present molecules as molecular switches.
Tetrahedron, 2005
In this paper, the synthesis of a crosslinkable co-polymer containing new pushpull arylethynyl z... more In this paper, the synthesis of a crosslinkable co-polymer containing new pushpull arylethynyl zinc porphyrins is described. The synthesis of porphyrin chromophores, analogous to Therien's porphyrin (J. Am. Chem. Soc. 1996, 118, 14971503) ...
Science, 2008
The translocation of biopolymers through pores and channels plays a fundamental role in numerous ... more The translocation of biopolymers through pores and channels plays a fundamental role in numerous biological processes. We describe here the mechanism of the threading of a series of polymer chains through a synthetic macrocycle, which mimics these natural processes. The threading of polymers involves a kinetically favorable "entron" effect, which is associated with the initial filling of the cavity by the end of the polymer. A preassociation between the outside of the macrocycle and the polymer induces a process in which the polymer end loops back into the cavity of the macrocycle. This looping mechanism results in accelerated threading rates and unidirectional motion and is reminiscent of the protein translocation through membrane pores.
Proceedings of the National Academy of Sciences, 2009
Calix[4]pyrroles having extended aromatic cavities have been functionalized with 4 ureas in the p... more Calix[4]pyrroles having extended aromatic cavities have been functionalized with 4 ureas in the para position of their meso phenyl substituents. This elaboration of the upper rim was completed in 2 synthetic steps starting from the ␣,␣,␣,␣-tetranitro isomer of the calix[4]pyrrole obtained in the acid catalyzed condensation of p-nitrophenyl methyl ketone and pyrrole. In dichloromethane solution and in the presence of 4,4-bipyridine N-N-dioxide the tetraurea calix[4]pyrrole dimerizes reversibly forming a cyclic array of 16 hydrogen bonds and encapsulating 1 molecule of bis-N-oxide. The encapsulated guest is bound in the cavity by hydrogen bonding to the 2 endohedral calix[4]pyrrole centers. Further evidence for dimerization of the tetraurea calix[4]pyrroles is provided by 1 H-NMR experiments and by the formation of mixed capsules.
Polymer Chemistry, 2012
An original and mild bromination protocol allows a poly-(hydroxyethyl acrylate) polymer synthesiz... more An original and mild bromination protocol allows a poly-(hydroxyethyl acrylate) polymer synthesized by ATRP to be converted readily and quantitatively into its corresponding poly-(bromoethyl acrylate) analogue. We show that the latter can be used as a common precursor towards ionic-liquid containing polymers.
Organic & Biomolecular Chemistry, 2012
A molecular engineering strategy based on rational variations of the bromine substitution pattern... more A molecular engineering strategy based on rational variations of the bromine substitution pattern in two-photon absorbing singlet oxygen sensitizers allows studying the relations that exist between the positioning of an inter-system crossing promoter on the charge-transfer chromophore and its ability to generate singlet oxygen.
New Journal of Chemistry, 2012
A simple polymerisation strategy allows water solubilisation of chromophores for biophotonics, wi... more A simple polymerisation strategy allows water solubilisation of chromophores for biophotonics, with good conservation of their fluorescence quantum-yield. Preliminary investigations show that the resulting objects are valuable candidates for photodynamic therapy and two-photon fluorescence imaging.
Journal of the American Chemical Society, 2010
Natural proteins and enzymes have been widely used as blueprints for the construction of syntheti... more Natural proteins and enzymes have been widely used as blueprints for the construction of synthetic catalysts. 1 As mimics for the monooxygenase cytochrome P450, myriads of modifications have been introduced into the skeleton of catalytic porphyrins with the purpose to improve the degree of control over the catalytic reactions and to reach efficiencies comparable to that of natural enzymes. 2 For example, nitrogen containing axial ligands have been used to enhance the rate of oxidation catalysts by activating the manganese-oxygen bond of Mn(III) porphyrins; 3 electron donating or withdrawing groups of different nature have been added to the meso positions of these porphyrins to tune the electronic properties; i.e. the reactivity of the catalytic center; 4 and shape-selective or chiral binding pockets have been introduced to improve the chemoand stereoselectivities of the reaction. 5 Furthermore, bulky substituents have been attached to the porphyrin to provide spatial shielding, thus preventing deactivation of the catalyst by dimerization reactions. We have previously reported on the synthesis and study of a diphenylglycoluril-appended porphyrin catalyst Mn2 . Because of its open ring structure, this compound is capable of binding to a polymer chain, e.g. polybutadiene, and thread on it. 8 Kinetic studies have revealed that the catalyst can convert the double bonds of polybutadiene into epoxide functions while gliding along the polymer chain in a pseudorotaxane fashion 9 ). Because of this unique feature, this catalyst can be called a processive enzyme mimic. 10 In spite of the very promising results in terms of guest complexation, motion along the polymer chain, and oxidation of polymer substrates, the system has some drawbacks hampering its practical use as a processive catalyst. For instance, a large excess of a bulky coordinating ligand (a pyridine derivative) is required to efficiently shield the outer face of the catalyst, thereby facilitating the catalytic reaction to take place on the inside through a rotaxane mechanism. However, even at high concentrations of axial ligand, the outer face of the catalyst remained partially accessible, and as a result deactivation of the catalyst, probably by a dimerization reaction, still occurred. This led to premature stalling of the epoxidation process.