scholarly journals Solvatomorph and polymorph screening of clopamide drug and its copper(ii) complex crystals

CrystEngComm ◽  
2021 ◽  
Author(s):  
G. Tamás Gál ◽  
Nóra V. May ◽  
László Trif ◽  
Judith Mihály ◽  
Petra Bombicz
Keyword(s):  
Copper Complexes ◽  
Polymorphic Modifications ◽  
Complex Crystals ◽  
First Time ◽  
Polymorph Screening

The anhydrate and hemihydrate structures of the marketed drug, clopamide, are described the first time. Structural landscape of its copper complexes is presented: three polymorphic modifications and an isostructural series of its alcohol clathrates.

scholarly journals Cyclam-Based Chelators Bearing Phosphonated Pyridine Pendants for 64Cu-PET Imaging : Synthesis, Physico-Chemical Studies, Radiolabeling and Bioimaging.

2020 ◽  
Author(s):  
Richard Knighton ◽  
Thibault Troadec ◽  
Valerie Mazan ◽  
Patricia La Saëc ◽  
Séverine Marionneau-Lambot ◽  
...  
Keyword(s):  
Pet Imaging ◽  
Copper Complexes ◽  
The Body ◽  
Renal Elimination ◽  
X Ray Diffraction ◽  
Physico Chemical ◽  
Chemical Studies ◽  
First Time ◽  
Excellent Stability

Herein we present the preparation of two novel cyclam-based macrocycles (te1pyp and cb-te1pyp), bearing phosphonate-appended pyridine side-arms for the coordination of copper(II) ions in the context of 64Cu PET imaging. The two ligands have been prepared through conventional protection-alkylation sequences on cyclam, and their coordination properties have been thoroughly investigated. The corresponding copper complexes have been fully characterized in the solid-state (X-Ray diffraction analysis) and in solution (EPR and UV-Vis spectroscopies). Potentiometric studies, combined with spectrometry, have also allowed us to determine their thermodynamic stability constants, confirming their high affinity for copper(II) cations. The kinetic inertness of the complexes has also been verified by acid-assisted dissociation experiments, enabling their use in 64Cu-PET imaging in mice for the first time. Indeed, the two ligands could be quantitatively radiolabeled under mild conditions, and the resulting 64Cu complexes have demonstrated excellent stability in serum. PET imaging demon-strated a set of features emerging from the combination of picolinates and phosphonate units: high stability in vivo, fast clear-ance from the body via renal elimination, and most interestingly, very low fixation in the liver. The latter is in contrast with what was observed for monopicolinate cyclam (te1pa), that had a non-negligible accumulation in the liver, owing probably to its different charge and lipophillicity. These results thus pave the way for the use of such phosphonated pyridine chelators for in vivo 64Cu-PET imaging.

scholarly journals Cyclam-Based Chelators Bearing Phosphonated Pyridine Pendants for 64Cu-PET Imaging : Synthesis, Physico-Chemical Studies, Radiolabeling and Bioimaging.

2020 ◽  
Author(s):  
Richard Knighton ◽  
Thibault Troadec ◽  
Valerie Mazan ◽  
Patricia La Saëc ◽  
Séverine Marionneau-Lambot ◽  
...  
Keyword(s):  
Pet Imaging ◽  
Copper Complexes ◽  
The Body ◽  
Renal Elimination ◽  
X Ray Diffraction ◽  
Physico Chemical ◽  
Chemical Studies ◽  
First Time ◽  
Excellent Stability

Herein we present the preparation of two novel cyclam-based macrocycles (te1pyp and cb-te1pyp), bearing phosphonate-appended pyridine side-arms for the coordination of copper(II) ions in the context of 64Cu PET imaging. The two ligands have been prepared through conventional protection-alkylation sequences on cyclam, and their coordination properties have been thoroughly investigated. The corresponding copper complexes have been fully characterized in the solid-state (X-Ray diffraction analysis) and in solution (EPR and UV-Vis spectroscopies). Potentiometric studies, combined with spectrometry, have also allowed us to determine their thermodynamic stability constants, confirming their high affinity for copper(II) cations. The kinetic inertness of the complexes has also been verified by acid-assisted dissociation experiments, enabling their use in 64Cu-PET imaging in mice for the first time. Indeed, the two ligands could be quantitatively radiolabeled under mild conditions, and the resulting 64Cu complexes have demonstrated excellent stability in serum. PET imaging demon-strated a set of features emerging from the combination of picolinates and phosphonate units: high stability in vivo, fast clear-ance from the body via renal elimination, and most interestingly, very low fixation in the liver. The latter is in contrast with what was observed for monopicolinate cyclam (te1pa), that had a non-negligible accumulation in the liver, owing probably to its different charge and lipophillicity. These results thus pave the way for the use of such phosphonated pyridine chelators for in vivo 64Cu-PET imaging.

From Prochiral N-Heterocyclic Carbenes (NHC) to Optically Pure Copper Complexes: New Opportunities in Asymmetric Catalysis

2019 ◽  
Author(s):  
Lingyu Kong ◽  
Jennifer Morvan ◽  
Delphine Pichon ◽  
Marion Jean ◽  
Muriel Albalat ◽  
...  
Keyword(s):  
Asymmetric Catalysis ◽  
Copper Complexes ◽  
Pure Copper ◽  
Heterocyclic Carbenes ◽  
Allylic Alkylation ◽  
Chiral Hplc ◽  
Pure Cu ◽  
First Time ◽  
Optically Pure ◽  
Cu Complexes

Well-defined optically pure copper-complexes are obtained from prochiral N- Heterocyclic Carbene (NHC) ligands. As predicted by DFT calculations, our strategy capitalizes on the formation of a metal-carbene bond which induces axial chirality. Configurationally stable (Sa)- and (Ra)-atropisomers of various Cu-complexes are isolated by preparative chiral HPLC in nearly quantitative yields and excellent optical purities (>99.5%). Their catalytic performances are illustrated in asymmetric allylic alkylation with high regioselectivity and enantioinductions. Importantly, the carbene transfer from an optically pure Cu-complex to gold or palladium center reveals, for the first time, a full stereoretentivity, supporting the hypothesis of an associative mechanism for the transmetalation.

Identification of Oxidized Chlorophylls and Metallochlorophyllic Complexes of Copper in Table Olives (cv. Gordal) with Green Staining Alteration

1999 ◽  
Vol 62 (10) ◽  
pp. 1172-1177 ◽  
Author(s):  
BEATRIZ GANDUL-ROJAS ◽  
LOURDES GALLARDO-GUERRERO ◽  
M. ISABEL MÍNGUEZ-MOSQUERA
Keyword(s):  
Molecular Mass ◽  
Copper Complexes ◽  
Fruits And Vegetables ◽  
Glyoxylic Acid ◽  
Table Olives ◽  
Chlorophyll Derivative ◽  
Spectroscopic Characteristics ◽  
First Time ◽  
Layer Chromatography

In Spanish green table olives showing the alteration known as green staining, new chlorophyll derivatives have been identified: the copper complexes of 31,32-didehydrorhodochlorin-15-glyoxylic acid-173-phytyl ester a and b (Cu-15-glyoxylic acid pheophytins a and b), and 31,32-didehydro-151-hydroxy-151-hydroxyrhodochlorin-15-acetic acid δ-lactone-152-methyl-173-phytyl ester a and b (Cu-151-OH-lactone-pheophytins a and b). These compounds were isolated by normal phase thin-layer chromatography and identified from their UV–visible and mass spectra and by co-chromatography with authentic standards. The chromatographic and spectroscopic characteristics and the molecular mass for a new allomerized chlorophyll derivative and its copper complex are reported. The corresponding molecular structure according to the molecular mass has been proposed. The characterization of the latter compounds enables their possible detection in processed fruits and vegetables. The present work gathers new advances in the study of the color alteration in table olives and this is the first time that copper complexes of oxidized chlorophylls are detected in foodstuffs.

Effect of Mn Doping on Magnetic and Dielectric Properties of Bi2Sn2O7

2015 ◽  
Vol 233-234 ◽  
pp. 105-108 ◽  
Author(s):  
Lubov V. Udod ◽  
Sergey S. Aplesnin ◽  
Maxim N. Sitnikov ◽  
Evgenii V. Eremin ◽  
Maxim S. Molokeev
Keyword(s):  
Electrical Resistance ◽  
Solid Phase Synthesis ◽  
Solid Phase ◽  
Phase Synthesis ◽  
Martensitic Phase Transitions ◽  
Polymorphic Modifications ◽  
Temperature Dependences ◽  
Magnetic And Dielectric Properties ◽  
First Time ◽  
Magnetic Dielectric

The Bi2(Sn0.95Mn0.05)2O7 compound existing simultaneously in two polymorphic modifications, namely, orthorhombic and cubic has been synthesized for the first time by solid-phase synthesis. The magnetic, dielectric and electrical properties of the compound have been studied. Anomalies in the temperature dependences of the electrical resistance and magnetic propoties have been found. These features are explained as martensitic phase transitions.

Syntheses and Properties of Cycloamidines Based on 4H-Imidazoles

2006 ◽  
Vol 61 (4) ◽  
pp. 437-447 ◽  
Author(s):  
Rainer Beckert ◽  
Catharina Hippius ◽  
Tillmann Gebauer ◽  
Frances Stöckner ◽  
Christina Lüdigk ◽  
...  
Keyword(s):  
Copper Complexes ◽  
Formation Constant ◽  
Formation Constants ◽  
Stable Complex ◽  
Single Electron Transfer ◽  
H Nmr ◽  
Reduction Potentials ◽  
Donor Acceptor ◽  
First Time ◽  
Derivatives Of

Employing three different syntheses a broad spectrum of 4H-imidazoles 3a - 3s has been synthesized. In the course of the two-fold aminolysis reaction leading to derivatives 3q - 3s, deeply colored byproducts could be isolated and structural characterized.These novel donor-acceptor derivatives of type 7 consist of an 1H- and 4H-imidazole which are connected by a nitrogen bridge and rearrange via rapid 1,3-/1,5-hydride shifts. Using 1H NMR experiments the aminolysis product 3p shows prototropic isomers which could be detected in equilibrium for the first time. Cyclovoltammetric measurements of a series of substituted 2-aryl derivatives 3d - 3i displayed two reversible single electron transfer steps with relatively small semiquinone formation constants between 102 and 4×103. The 4H-imidazole 3d was successfully converted into boratetraaza-pentalene 8a, which showed two well separated reduction potentials. The value of semiquinone formation constant of 8a (1.8×1015) is even higher than those reported for similar derivatives. 4H-imidazoles can also be employed for the efficient complexation of catalytically important metals as exemplified by copper complexes 11 and 12. Derivative 3m, which possesses an additional chelating pyridine substructure, formed a stable complex of structural composition Zn(3m)2 with diethyl zinc

scholarly journals Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and their Photoluminescence

2020 ◽  
Author(s):  
Marius Klein ◽  
Nemrud Demirel ◽  
Alexander Schinabeck ◽  
Hartmut Yersin ◽  
Jörg Sundermeyer
Keyword(s):  
Room Temperature ◽  
Copper Complexes ◽  
Structural Information ◽  
Uv Light ◽  
Quantum Yields ◽  
Dinuclear Copper ◽  
Mononuclear Complexes ◽  
Base Form ◽  
The Common ◽  
First Time

A series of dinuclear copper(I) N,C,N- and P,C,P-carbodiphosphorane (CDP) complexes using multidentate ligands CDP(Py)2 (1) and (CDP(CH2PPh2)2 (13) have been isolated and characterized. Detailed structural information was gained by single crystal XRD analyses of nine representative examples. The common structural motive is the central double ylidic carbon atom with its characteristic two lone-pairs involved into binding of two geminal L-Cu(I) fragments at Cu-Cu distances in the range 2.55 – 2.67 Å. In order to enhance conformational rigidity within the characteristic Cu-C-Cu triangle, two types of chelating side arms were symmetrically attached to each phosphorus atom: two 2-pyridyl functions in ligand CDP(Py)2 (1) and its dinuclear copper complexes 2-9 and 11, as well as two diphenylphosphinomethylene functions in ligand CDP(CH2PPh2)2 (13) and its di- and mononuclear complexes 14-18. Neutral complexes were typically obtained via reaction of 1 with Cu(I) species CuCl, CuI, and CuSPh or via salt elimination reaction of [(CuCl)2(CDP(Py)2] (2) with sodium carbazolate. Cationic Cu(I) complexes were prepared upon treating 1 with two equivalents of [Cu(NCMe)4]PF6, followed by the addition of either two equivalent of an aryl phosphine (PPh3, P(C6H4OMe)3) or one equivalent of a bisphosphine ligands DPEPhos, XantPhos or dppf. For the first time carbodiphosphorane CDP(CH2PPh2)2 (13) could be isolated upon treating its precursor [CH(dppm)2]Cl (12) with NaNH2 in liquid NH3. A protonated and a deprotonated derivative of ligand 13 were prepared and their coordination was compared to neutral CDP ligand 13. NMR analysis and DFT calculations reveal, that the most stable tautomer of 13 does not show a CDP (or carbone) structure in its uncoordinated base form. For most of the prepared complexes, photoluminescence upon irradiation with UV light at room temperature was observed. Quantum yields (PL) were determined to 36% for dicationic [(CuPPh3)2(CDP(Py)2)](PF6)2 (4) and to 60% for neutral [(CuSPh)2(CDP(CH2PPh2)2] (16).

From Prochiral N-Heterocyclic Carbenes (NHC) to Optically Pure Copper Complexes: New Opportunities in Asymmetric Catalysis

2019 ◽  
Author(s):  
Lingyu Kong ◽  
Jennifer Morvan ◽  
Delphine Pichon ◽  
Marion Jean ◽  
Muriel Albalat ◽  
...  
Keyword(s):  
Asymmetric Catalysis ◽  
Copper Complexes ◽  
Pure Copper ◽  
Heterocyclic Carbenes ◽  
Allylic Alkylation ◽  
Chiral Hplc ◽  
Pure Cu ◽  
First Time ◽  
Optically Pure ◽  
Cu Complexes

Well-defined optically pure copper-complexes are obtained from prochiral N- Heterocyclic Carbene (NHC) ligands. As predicted by DFT calculations, our strategy capitalizes on the formation of a metal-carbene bond which induces axial chirality. Configurationally stable (Sa)- and (Ra)-atropisomers of various Cu-complexes are isolated by preparative chiral HPLC in nearly quantitative yields and excellent optical purities (>99.5%). Their catalytic performances are illustrated in asymmetric allylic alkylation with high regioselectivity and enantioinductions. Importantly, the carbene transfer from an optically pure Cu-complex to gold or palladium center reveals, for the first time, a full stereoretentivity, supporting the hypothesis of an associative mechanism for the transmetalation.

scholarly journals Cu(I) Complexes of Multidentate N,C,N- and P,C,P-Carbodiphosphorane Ligands and Their Photoluminescence

Molecules ◽  
2020 ◽  
Vol 25 (17) ◽  
pp. 3990 ◽  
Author(s):  
Marius Klein ◽  
Nemrud Demirel ◽  
Alexander Schinabeck ◽  
Hartmut Yersin ◽  
Jörg Sundermeyer
Keyword(s):  
Room Temperature ◽  
Copper Complexes ◽  
Structural Information ◽  
Uv Light ◽  
Quantum Yields ◽  
Dinuclear Copper ◽  
Mononuclear Complexes ◽  
Base Form ◽  
The Common ◽  
First Time

A series of dinuclear copper(I) N,C,N- and P,C,P-carbodiphosphorane (CDP) complexes using multidentate ligands CDP(Py)2 (1) and (CDP(CH2PPh2)2 (13) have been isolated and characterized. Detailed structural information was gained by single-crystal XRD analyses of nine representative examples. The common structural motive is the central double ylidic carbon atom with its characteristic two lone pairs involved in the binding of two geminal L-Cu(I) fragments at Cu–Cu distances in the range 2.55–2.67 Å. In order to enhance conformational rigidity within the characteristic Cu–C–Cu triangle, two types of chelating side arms were symmetrically attached to each phosphorus atom: two 2-pyridyl functions in ligand CDP(Py)2 (1) and its dinuclear copper complexes 2–9 and 11, as well as two diphenylphosphinomethylene functions in ligand CDP(CH2PPh2)2 (13) and its di- and mononuclear complexes 14–18. Neutral complexes were typically obtained via the reaction of 1 with Cu(I) species CuCl, CuI, and CuSPh or via the salt elimination reaction of [(CuCl)2(CDP(Py)2] (2) with sodium carbazolate. Cationic Cu(I) complexes were prepared upon treating 1 with two equivalents of [Cu(NCMe)4]PF6, followed by the addition of either two equivalents of an aryl phosphine (PPh3, P(C6H4OMe)3) or one equivalent of bisphosphine ligands bis[(2-diphenylphosphino)phenyl] ether (DPEPhos), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (XantPhos), or 1,1′-bis(diphenyl-phosphino) ferrocene (dppf). For the first time, carbodiphosphorane CDP(CH2PPh2)2 (13) could be isolated upon treating its precursor [CH(dppm)2]Cl (12) with NaNH2 in liquid NH3. A protonated and a deprotonated derivative of ligand 13 were prepared, and their coordination was compared to neutral CDP ligand 13. NMR analysis and DFT calculations reveal that the most stable tautomer of 13 does not show a CDP (or carbone) structure in its uncoordinated base form. For most of the prepared complexes, photoluminescence upon irradiation with UV light at room temperature was observed. Quantum yields (ΦPL) were determined to be 36% for dicationic [(CuPPh3)2(CDP(Py)2)](PF6)2 (4) and 60% for neutral [(CuSPh)2(CDP(CH2PPh2)2] (16).

Discotic liquid crystals of transition metal complexes 39: columnar mesomorphism and homeotropic alignment speed of sandwich-type of double-deckers and triple-deckers based on phthalocyaninato lutetium metal complexes

2007 ◽  
Vol 11 (12) ◽  
pp. 846-856 ◽  
Author(s):  
Hidetomo Mukai ◽  
Kazuaki Hatsusaka ◽  
Kazuchika Ohta
Keyword(s):  
Metal Complexes ◽  
Liquid Crystalline ◽  
Copper Complexes ◽  
X Ray Diffraction ◽  
Large Area ◽  
Temperature Dependent ◽  
Scanning Calorimetry ◽  
Sandwich Type ◽  
Homeotropic Alignment ◽  
First Time

A series of sandwich-type metal complexes, bis[2,3,9,10,16,17,23,24-octakis(3,4-dialkoxyphenoxy)phthalocyaninato]lutetium(III) ({[( C n O )2 PhO ]8 Pc }2 Lu (n = 8−16): double-deckers (2)), were synthesized. As the by-product, tris[2,3,9,10,16,17,23,24-octakis(3,4-diakoxyphenoxy)phthalocyaninato]dilutetium(III) ({[( C n O )2 PhO ]8 Pc }3 Lu 2 (n = 8, 9, 11, 12, 14, 16): triple-deckers (3)) were successfully separated. The mesomorphic properties of these double-deckers (2) and triple-deckers (3) were investigated using a polarization microscope, differential scanning calorimetry and temperature-dependent X-ray diffraction techniques. The double-deckers (2) showed Colh , Cub and Coltet mesophases for n ≥ 10. On the other hand, the triple-deckers (3) showed only a Colr mesophase for n = 8, only a Coltet mesophase for n = 14, and both Colr and Coltet mesophases for n = 9, 11, 12 and 16. For the Coltet mesophase, both the double-deckers (2) and the triple-deckers (3) exhibited spontaneous homeotropic alignment in a large area. In comparison with the homeotropic alignment of these present lutetium complexes 2, 3 and the previous copper complexes, 2,3,9,10,16,17,23,24-octakis(3,4-dialkoxyphenoxy)phthalocyaninato copper(II) ([( C n O )2 PhO ]8 PcCu (n = 9-14): single-decker (1)), the alignment was fast, slow and fast, respectively, in the order of the single-deckers (1), double-deckers (2) and triple-deckers (3). Very interestingly, the complexes 1 and 3 which have flat Pc macrocycles gave fast alignment, whereas the complexes, 2, which have non-flat Pc macrocycles, gave slow alignment. Thus, it was revealed for the first time that the flatness of discotic liquid crystalline molecules influences the speed of homeotropic alignment.

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