PGMB
- Research Themes
- People
- Publications
Coordination: Dr. Laurence Grimaud
The team Peptides, Glycoconjugates and Metals in Biology is constituted of organic and inorganic chemists who share skills, and know-hows to synthesize and study the reactivity of bioactive molecules, bioconjugates and functional nanoparticles.
Combining organic synthesis, spectroscopies (IR, UV-Vis absorption, fluorescence, X-fluorescence) electrochemistry and biology, the research of the team is aimed at deciphering the reactivity and properties of bioinspired constructs ranging from the molecular to the supramolecular and colloidal scales. Applications include the fundamental understanding of the (bio)catalytic activity of metals complexes, the study of biomolecular interactions (membrane, peptides, proteins and glycoconjugates) and cellular imaging using tailored fluorescent, IR or X-fluorescent probes.
Affiliation: ED 406: Molecular Chemistry Paris-Centre
Research
 Bioinorganic Chemistry |
 Bioorganic Chemistry |
 |
2019 |
Electroactive fluorescent false neurotransmitter FFN102 partially replaces dopamine in PC12 cell vesicles Article de journal L Hu; A Savy; L Grimaud; M Guille-Collignon; F Lemaître; C Amatore; J Delacotte Biophysical Chemistry, 245 , p. 1–5, 2019. @article{Hu:2019, title = {Electroactive fluorescent false neurotransmitter FFN102 partially replaces dopamine in PC12 cell vesicles}, author = {L Hu and A Savy and L Grimaud and M Guille-Collignon and F Lemaître and C Amatore and J Delacotte}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85057201704&doi=10.1016%2fj.bpc.2018.11.001&partnerID=40&md5=28655b4c152ce0fc51fc037feefcff97}, doi = {10.1016/j.bpc.2018.11.001}, year = {2019}, date = {2019-01-01}, journal = {Biophysical Chemistry}, volume = {245}, pages = {1--5}, abstract = {In the last decade, following fluorescent dyes and protein tags, pH sensitive false fluorescent neurotransmitters (FFN) were introduced and were valuable for labeling secretory vesicles and monitoring exocytosis at living cells. In particular, the synthetic analog of neurotransmitters FFN102 was shown to be an electroactive probe. Here, we show that FFN102 is suitable to be used as a bioanalytic probe at the widely used PC12 cell model. FFN102 was uptaken in the secretory vesicles of PC12 cells, partially replacing the endogenous dopamine stored in these vesicles. The different oxidation potentials of dopamine and FFN102 allowed to determine that ca. 12% of dopamine was replaced by FFN102. Moreover, the FFN102 was found to be over released through the initial fusion pore suggesting that it was mostly uptaken in fast diffusion compartment of the vesicles. © 2018 Elsevier B.V.}, keywords = {}, pubstate = {published}, tppubtype = {article} } In the last decade, following fluorescent dyes and protein tags, pH sensitive false fluorescent neurotransmitters (FFN) were introduced and were valuable for labeling secretory vesicles and monitoring exocytosis at living cells. In particular, the synthetic analog of neurotransmitters FFN102 was shown to be an electroactive probe. Here, we show that FFN102 is suitable to be used as a bioanalytic probe at the widely used PC12 cell model. FFN102 was uptaken in the secretory vesicles of PC12 cells, partially replacing the endogenous dopamine stored in these vesicles. The different oxidation potentials of dopamine and FFN102 allowed to determine that ca. 12% of dopamine was replaced by FFN102. Moreover, the FFN102 was found to be over released through the initial fusion pore suggesting that it was mostly uptaken in fast diffusion compartment of the vesicles. © 2018 Elsevier B.V. |
From Benzofurans to Indoles: Palladium-Catalyzed Reductive Ring-Opening and Closure via β-Phenoxide Elimination Article de journal L A Perego; S Wagschal; R Grüber; P Fleurat-Lessard; L El Kaïm; L Grimaud Advanced Synthesis and Catalysis, 361 (1), p. 151–159, 2019. @article{Perego:2019, title = {From Benzofurans to Indoles: Palladium-Catalyzed Reductive Ring-Opening and Closure via β-Phenoxide Elimination}, author = {L A Perego and S Wagschal and R Grüber and P Fleurat-Lessard and L El Kaïm and L Grimaud}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85057441313&doi=10.1002%2fadsc.201801225&partnerID=40&md5=56673a99ee9fc8c525272edb560d0ecc}, doi = {10.1002/adsc.201801225}, year = {2019}, date = {2019-01-01}, journal = {Advanced Synthesis and Catalysis}, volume = {361}, number = {1}, pages = {151--159}, abstract = {Benzofurans can undergo ring-opening by a palladium-catalyzed process resulting in C−O bond breaking. Benzofuran-tethered 2-iodoanilines give synthetically interesting 2-(3-indolylmethyl)phenols in an overall reductive process. Mechanistic studies suggest that this unusual reaction proceeds by carbopalladation of benzofuran giving a 3-palladated 2,3-dihydrobenzofuran intermediate, which then fragments by an uncommon trans-elimination of the phenoxide group β to the metal. In this transformation, N,N-diisopropylethylamine (DIPEA) acts as a base and as a reducing agent: it regenerates palladium(0) from palladium(II), thus allowing catalytic turnover. (Figure presented.). © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim}, keywords = {}, pubstate = {published}, tppubtype = {article} } Benzofurans can undergo ring-opening by a palladium-catalyzed process resulting in C−O bond breaking. Benzofuran-tethered 2-iodoanilines give synthetically interesting 2-(3-indolylmethyl)phenols in an overall reductive process. Mechanistic studies suggest that this unusual reaction proceeds by carbopalladation of benzofuran giving a 3-palladated 2,3-dihydrobenzofuran intermediate, which then fragments by an uncommon trans-elimination of the phenoxide group β to the metal. In this transformation, N,N-diisopropylethylamine (DIPEA) acts as a base and as a reducing agent: it regenerates palladium(0) from palladium(II), thus allowing catalytic turnover. (Figure presented.). © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim |
Methylglyoxal, a potent inducer of AGEs, connects between diabetes and cancer Article de journal J Bellier; M -J Nokin; E Lardé; P Karoyan; O Peulen; V Castronovo; A Bellahcène Diabetes Research and Clinical Practice, 148 , p. 200–211, 2019. @article{Bellier:2019, title = {Methylglyoxal, a potent inducer of AGEs, connects between diabetes and cancer}, author = {J Bellier and M -J Nokin and E Lardé and P Karoyan and O Peulen and V Castronovo and A Bellahcène}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85060445406&doi=10.1016%2fj.diabres.2019.01.002&partnerID=40&md5=0f0783fde807776888c9436e0430c762}, doi = {10.1016/j.diabres.2019.01.002}, year = {2019}, date = {2019-01-01}, journal = {Diabetes Research and Clinical Practice}, volume = {148}, pages = {200--211}, abstract = {Diabetes is one of the most frequent diseases throughout the world and its incidence is predicted to exponentially progress in the future. This metabolic disorder is associated with major complications such as neuropathy, retinopathy, atherosclerosis, and diabetic nephropathy, the severity of which correlates with hyperglycemia, suggesting that they are triggered by high glucose condition. Reducing sugars and reactive carbonyl species such as methylglyoxal (MGO) lead to glycation of proteins, lipids and DNA and the gradual accumulation of advanced glycation end products (AGEs) in cells and tissues. While AGEs are clearly implicated in the pathogenesis of diabetes complications, their potential involvement during malignant tumor development, progression and resistance to therapy is an emerging concept. Meta-analysis studies established that patients with diabetes are at higher risk of developing cancer and show a higher mortality rate than cancer patients free of diabetes. In this review, we highlight the potential connection between hyperglycemia-associated AGEs formation on the one hand and the recent evidence of pro-tumoral effects of MGO stress on the other hand. We also discuss the marked interest in anti-glycation compounds in view of their strategic use to treat diabetic complications but also to protect against augmented cancer risk in patients with diabetes. © 2019}, keywords = {}, pubstate = {published}, tppubtype = {article} } Diabetes is one of the most frequent diseases throughout the world and its incidence is predicted to exponentially progress in the future. This metabolic disorder is associated with major complications such as neuropathy, retinopathy, atherosclerosis, and diabetic nephropathy, the severity of which correlates with hyperglycemia, suggesting that they are triggered by high glucose condition. Reducing sugars and reactive carbonyl species such as methylglyoxal (MGO) lead to glycation of proteins, lipids and DNA and the gradual accumulation of advanced glycation end products (AGEs) in cells and tissues. While AGEs are clearly implicated in the pathogenesis of diabetes complications, their potential involvement during malignant tumor development, progression and resistance to therapy is an emerging concept. Meta-analysis studies established that patients with diabetes are at higher risk of developing cancer and show a higher mortality rate than cancer patients free of diabetes. In this review, we highlight the potential connection between hyperglycemia-associated AGEs formation on the one hand and the recent evidence of pro-tumoral effects of MGO stress on the other hand. We also discuss the marked interest in anti-glycation compounds in view of their strategic use to treat diabetic complications but also to protect against augmented cancer risk in patients with diabetes. © 2019 |
Glycoreplica peptides to investigate molecular mechanisms of immune-mediated physiological versus pathological conditions Article de journal A Mazzoleni; J -M Mallet; P Rovero; A M Papini Archives of Biochemistry and Biophysics, 663 , p. 44–53, 2019. @article{Mazzoleni:2019, title = {Glycoreplica peptides to investigate molecular mechanisms of immune-mediated physiological versus pathological conditions}, author = {A Mazzoleni and J -M Mallet and P Rovero and A M Papini}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85059303265&doi=10.1016%2fj.abb.2018.12.030&partnerID=40&md5=054e28b7f9071c163b4af5dcba3d2fcd}, doi = {10.1016/j.abb.2018.12.030}, year = {2019}, date = {2019-01-01}, journal = {Archives of Biochemistry and Biophysics}, volume = {663}, pages = {44--53}, abstract = {Investigation of the role of saccharides and glycoconjugates in mechanisms of immune-mediated physiological and pathological conditions is a hot topic. In fact, in many autoimmune diseases cross-reactivity between sugar moieties exposed on exogenous pathogens and self-molecules has long been hinted. Several peptides have been reported as mimetics of glycans specifically interacting with sugar-binding antibodies. The seek for these glycoreplica peptides is instrumental in characterizing antigen mimicry pathways and their involvement in triggering autoimmunity. Therefore, peptides mimicking glycan-protein interactions are valuable molecular tools to overcome the difficulties of oligosaccharide preparations. The clinical impact of peptide-based probes for autoimmune diseases diagnosis and follow-up is emerging only recently as just the tip of the iceberg of an overlooked potential. Here we provide a brief overview of the relevance of the structural and functional aspects of peptide probes and their mimicry effect in autoimmunity mechanisms for promising applications in diagnostics and therapeutics. © 2019 Elsevier Inc.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Investigation of the role of saccharides and glycoconjugates in mechanisms of immune-mediated physiological and pathological conditions is a hot topic. In fact, in many autoimmune diseases cross-reactivity between sugar moieties exposed on exogenous pathogens and self-molecules has long been hinted. Several peptides have been reported as mimetics of glycans specifically interacting with sugar-binding antibodies. The seek for these glycoreplica peptides is instrumental in characterizing antigen mimicry pathways and their involvement in triggering autoimmunity. Therefore, peptides mimicking glycan-protein interactions are valuable molecular tools to overcome the difficulties of oligosaccharide preparations. The clinical impact of peptide-based probes for autoimmune diseases diagnosis and follow-up is emerging only recently as just the tip of the iceberg of an overlooked potential. Here we provide a brief overview of the relevance of the structural and functional aspects of peptide probes and their mimicry effect in autoimmunity mechanisms for promising applications in diagnostics and therapeutics. © 2019 Elsevier Inc. |
2018 |
Rhenium tricarbonyl complexes with arenethiolate axial ligands Article de journal M He; H Y V Ching; C Policar; H C Bertrand New Journal of Chemistry, 42 (14), p. 11312–11323, 2018. @article{He:2018, title = {Rhenium tricarbonyl complexes with arenethiolate axial ligands}, author = {M He and H Y V Ching and C Policar and H C Bertrand}, url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85049750977&doi=10.1039%2fc8nj01960f&partnerID=40&md5=eac4613cb3f849f5a149c72a46384912}, doi = {10.1039/c8nj01960f}, year = {2018}, date = {2018-01-01}, journal = {New Journal of Chemistry}, volume = {42}, number = {14}, pages = {11312--11323}, abstract = {Due to their unique electronic and photophysical properties, rhenium(i) fac-tricarbonyl complexes of general formula [Re(NtextasciicircumN)(CO)3X]n+ have been arousing constant interest in many diverse fields and applications, such as CO2 (photo)electroreduction, organic light emitting diodes and materials, sensors, biological applications and bio-imaging. The photophysical properties of [Re(NtextasciicircumN)(CO)3X]n+ complexes can be modulated by structural variations of the ligands. Modifications of the NtextasciicircumN diimine ligand and of the axial X ligand have been deeply investigated. However, thiolate ligands have scarcely been used in the synthesis of rhenium tricarbonyl complexes. We describe the synthesis of a series of Pyta and Tapy-based Re(i) fac-tricarbonyl complexes with diversely para-substituted arenethiolates in the coordination sphere and report on the electrochemical, photophysical properties and DFT studies of such complexes. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Due to their unique electronic and photophysical properties, rhenium(i) fac-tricarbonyl complexes of general formula [Re(NtextasciicircumN)(CO)3X]n+ have been arousing constant interest in many diverse fields and applications, such as CO2 (photo)electroreduction, organic light emitting diodes and materials, sensors, biological applications and bio-imaging. The photophysical properties of [Re(NtextasciicircumN)(CO)3X]n+ complexes can be modulated by structural variations of the ligands. Modifications of the NtextasciicircumN diimine ligand and of the axial X ligand have been deeply investigated. However, thiolate ligands have scarcely been used in the synthesis of rhenium tricarbonyl complexes. We describe the synthesis of a series of Pyta and Tapy-based Re(i) fac-tricarbonyl complexes with diversely para-substituted arenethiolates in the coordination sphere and report on the electrochemical, photophysical properties and DFT studies of such complexes. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. |