Papers by Giovanna Longhi
The Journal of Chemical Physics, 1988
The Raman spectrum in the CH stretching region of molecules containing long alkyl residues shows ... more The Raman spectrum in the CH stretching region of molecules containing long alkyl residues shows characteristic features which provide direct information on their molecular flexibility, as probed by the C–H stretching oscillator which vibrates on the picosecond time scale. From their Raman spectra, librational motions of the (CH2)n units can be studied for molecules in the solid and liquid phases.
Two triarylcorrole complexes, (hydroxy)[5,10,15tritolylcorrolato]silicon-(TTC)Si(OH) and (dihydro... more Two triarylcorrole complexes, (hydroxy)[5,10,15tritolylcorrolato]silicon-(TTC)Si(OH) and (dihydroxy)[5,10,15tritolylcorrolato]phosphorous-(TTC)P(OH) 2 , have been investigated by magnetic circular dichroism (MCD) and magnetic circularly polarized luminescence (MCPL). The spectroscopic investigations have been combined with explicit calculation of MCD response through time-dependent density functional theory (TD-DFT) formalism. This has allowed us to better define the role of molecular orbitals in the transitions associated with the Soret and Q bands. Besides and more importantly, MCD has made it possible to follow the titration process of (TTC)Si(OH) in dimethyl sulfoxide (DMSO) solution with NaF and of (TTC)P(OH) 2 in dichloromethane solution with alcohols in a complementary and, we dare say, more sensitive way with respect to absorption and fluorescence data. Finally, the MCPL spectra and the ancillary TD-DFT calculations have allowed us to characterize the excited state of (TTC)Si(OH).
Organic Chemistry Frontiers
Versatile enantiopure helical systems are described and are of interest owing to their intense ch... more Versatile enantiopure helical systems are described and are of interest owing to their intense chiroptical responses, their attractive architecture for metallosupramolecular chemistry and CISS effect.
Physical Chemistry Chemical Physics
The helical conformational equilibrium and aggregation of chiral biliverdin diester derivatives a... more The helical conformational equilibrium and aggregation of chiral biliverdin diester derivatives are sensitive to environmental physicochemical conditions such as pH, the presence of metal ions, and the length of the diester chain.
New Journal of Chemistry
Conformational chirality is a feature that may arise from the presence of a hindered rotation aro... more Conformational chirality is a feature that may arise from the presence of a hindered rotation around a single bond that corresponds to a stereogenic axis.
The Journal of Physical Chemistry B
UV−vis absorption and magnetic circular dichroism (MCD) spectra of octakis thioethyl "free base" ... more UV−vis absorption and magnetic circular dichroism (MCD) spectra of octakis thioethyl "free base" porphyrazine H 2 OESPz and its metal complexes MOESPz (M = Mg, Zn, Ni, Pd, Cu), as well as of [MnOESPz(SH)] were recorded. In the last case, MCD proved to have quite good sensitivity to the coordination of this complex with 1-methylimidazole (1-mim) in benzene. Time-dependent density functional theory (TDDFT) calculations were carried out for the considered porphyrazine complexes and showed good performance on comparing with MCD and UV−vis experimental spectra, even in the open-shell Cu and Mn cases. Calculations accounted for the red shift observed in the thioalkyl compounds and allowed us to reveal the role of sulfur atoms in spectroscopically relevant molecular orbitals and to highlight the importance of the conformations of the thioethyl external groups. Calculated MCD spectra of [MnOESPz(SH)] confirm the Mn(III) → Mn(II) redox process, which leads to the [Mn(OESPz)(1-mim) 2 ] species, and the relevance of the spin state for MCD is revealed.
Symmetry
Bicyclo[3.3.1]nonane-2,6-dione (1) and bicyclo[3.3.1]nona-3,7-diene-2,6-dione (2) have been exami... more Bicyclo[3.3.1]nonane-2,6-dione (1) and bicyclo[3.3.1]nona-3,7-diene-2,6-dione (2) have been examined by vibrational circular dichroism (VCD), which, as for most C2-symmetric systems, exhibits strong VCD signals. In the case of 2, VCD signals are stronger and sharper with several bisignate doublets; for 1, signals are less intense and broader. The VCD and IR spectra are excellently predicted by DFT calculations: only one conformer is present for 2, while for 1, three main conformers, related through concerted skeleton torsional motions are present (two of them being interchanged by C2-rotation). The VCD spectrum shows specific features for the different conformers, such that correct population factors are crucial for reproducing experimental data. Also, the TD-DFT prediction of ECD (electronic circular dichroism) spectra is good. By comparing the spectroscopic signature of the two molecules (both VCD and ECD) and by careful analysis of the theoretical results, the role of the C=C dou...
Applied Sciences
We re-examine the theory of electronic and vibrational circular dichroism spectroscopy in terms o... more We re-examine the theory of electronic and vibrational circular dichroism spectroscopy in terms of the formalism of frequency-dependent molecular polarizabilities. We show the link between Fermi’s gold rule in circular dichroism and the trace of the complex electric dipole–magnetic dipole polarizability. We introduce the C++ code polar to compute the molecular polarizability complex tensors from quantum chemistry outputs, thus simulating straightforwardly UV-visible absorption (UV-Vis)/electronic circular dichroism (ECD) spectra, and infrared (IR)/vibrational circular dichroism (VCD) spectra. We validate the theory and the code by referring to literature data of a large group of chiral molecules, showing the remarkable accuracy of density functional theory (DFT) methods. We anticipate the application of this methodology to the interpretation of vibrational spectra in various measurement conditions, even in presence of metal surfaces with plasmonic properties. Our theoretical develop...
Chemistry - A European Journal
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 2, 2018
Two new inherently chiral oligothiophenes characterized by the atropisomeric 3,3'-bithianapht... more Two new inherently chiral oligothiophenes characterized by the atropisomeric 3,3'-bithianaphtene scaffold functionalized with fused ring bithiophene derivatives, namely 4H-cyclopenta [2,1-b3:4b']dithiophene (CPDT) and dithieno[3,3-b:2',3'-d]pyrrole (DTP), were synthesized. The racemates were fully characterized and resolved into antipodes by enantioselective HPLC. The enantiomers were analyzed through different chiroptical techniques: electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) were employed to attribute the absolute configuration (AC). Comparison of experimental and calculated VCD spectra confirmed the DFT calculated conformational characteristics. The compound functionalized with two CPDT units was oxidized with FeCl3 and ECD and CPL of the resulting material were measured. Circularly Polarized Luminescence (CPL) was measured in order to verify if inherently chiral oligothiophenes could be promising systems for chiral photonics appl...
Chirality, 2018
The use of stereodynamic probes is becoming one of the leading strategies for the fast and effect... more The use of stereodynamic probes is becoming one of the leading strategies for the fast and effective determination of enantiomeric excess. Recently, we reported a series of novel molecular architectures based on a modified tris(2-pyridylmethyl)amine complex (TPMA), which are able to amplify the electronic CD, in the case of Zn(II) assemblies and vibrational CD, in the case of Co(II) assemblies. Herein, we report a structural modification of the ligand with the purpose to obtain a fluorescent chiral probe. The study deals with the synthesis of the novel ligand, the formation of the self-assembly system with amino acids, and the study of the electronic CD and circularly polarized luminescence.
Molecules (Basel, Switzerland), Jan 16, 2018
Taking into account the postulated reaction mechanism for the organocatalytic epoxidation of elec... more Taking into account the postulated reaction mechanism for the organocatalytic epoxidation of electron-poor olefins developed by our laboratory, we have investigated the key factors able to positively influence the H-bond network installed inside the substrate/catalyst/oxidizing agent. With this aim, we have: (i) tested a few catalysts displaying various effects that noticeably differ in terms of steric hindrance and electron demand; (ii) employed α-alkylidene oxindoles decorated with different substituents on the aromatic ring (-), the exocylic double bond (-), and the amide moiety (-). The observed results suggest that the modification of the electron-withdrawing group (EWG) weakly conditions the overall outcomes, and conversely a strong influence is unambiguously ascribable to either the -protected or -unprotected lactam framework. Specifically, when the NH free substrates (-) are employed, an inversion of the stereochemical control is observed, while the introduction of a Boc pro...
Chemistry (Weinheim an der Bergstrasse, Germany), Jan 21, 2018
A new family of homochiral silver complexes based on carbophilic interactions with ortho-phenylen... more A new family of homochiral silver complexes based on carbophilic interactions with ortho-phenylene ethynylene (o-OPE) scaffolds containing up to two silver atoms are described. These compounds represent a unique class of complexes with chirality at the metal. Chiral induction is based on the inclusion of chiral sulfoxides, which allow efficient transfer of chirality to the helically folded o-OPE, leading to circularly polarized luminescence (CPL)- and vibrational circular dichroism (VCD)-active compounds. In the presence of silver(I) cations, carbophilic interactions dominate, which promote helical structures with a defined helicity. This is one of the very scarce examples of the use of such interactions in the attractive field of abiotic foldamers. The switching event has been extensively studied by using different chiroptical techniques, including circular dichroism, CPL, and VCD, and represents one of the few CPL switches described in the literature.
Chirality, Jan 30, 2017
Vibrational and electronic circular dichroism (VCD and ECD) spectra of 3 optically active bilirub... more Vibrational and electronic circular dichroism (VCD and ECD) spectra of 3 optically active bilirubin analogs with propionic acid groups replaced by (1) 1-(S)-methylpropyl groups, (2) 3-acetoxy-1-(S)-methylpropyl groups, and (3) 1-(S)-2-(R)-dimethyl-2-(methoxycarbonyl)ethyl groups have been recorded at different concentrations in chloroform. The aliphatic chains attached to C-8 and C-12 of the 3 chosen mesobilirubins were modified so as to possess no OH group. The variation of the VCD spectra with concentration is consistent with the formation of dimers at high concentration. Density functional theory and time-dependent density functional theory calculations on monomeric and dimeric forms support such a conclusion. Comparing with previous VCD (ECD) and IR (UV) studies of other mesobilirubin molecules, it is concluded that here, the key feature for aggregation is the missing OH groups on the propionic acid chains. The latter, in synergy with the polar groups of lactam moieties, appear ...
Chirality, Jan 31, 2017
In this paper, we have studied the chiroptical properties of a family of o-oligo(phenyleneethynyl... more In this paper, we have studied the chiroptical properties of a family of o-oligo(phenyleneethynylene) (o-OPE) derivatives with different steric hindrance. Experimental results show high dissymmetry factors (gabs and glum up to 1.1 × 10-2 ) and very similar electronic circular dichroism (ECD) and circularly polarized luminescence (CPL) for all the derivatives that make this basic o-OPE scaffold a robust pure organic emitter. Vibrational circular dichroism spectra are used to characterize conformational properties in solution. Density functional theory and time-dependent density functional theory calculations support experimental results also proving that ECD and CPL are almost exclusively linked to helical moiety and not to size or conformation of substituents. As chiroptical properties of these emitters are independent of substituents, this OPE scaffold can be used as basic skeleton for the design of sensing probes with high CPL efficiencies.
Biochimica et biophysica acta, Nov 25, 2017
Ferritinophagy is the process of autophagic degradation of ferritin that participates in the regu... more Ferritinophagy is the process of autophagic degradation of ferritin that participates in the regulation of cellular iron homeostasis. This process was shown to be mediated by the selective cargo-receptor Nuclear Receptor Coactivator-4 (NCOA4) that binds ferritin and targets it to emerging autophagosome. To characterize some of the biochemical properties of the interaction between the two proteins we cloned and expressed in E. coli the ferritin-binding domain of human NCOA4, fragment 383-522. It was purified and subjected to biochemical analysis. The NCOA4(383-522) fragment was expressed in soluble and dimeric form, and CD spectra indicated low level of secondary structure. The Ferritin binding activity of the fragment was investigated by developing an electrophoretic mobility shift and an ELISA assays. They showed that the NCOA4 fragment binds the H-ferritin with an affinity in the nM range, but not the R23A H-ferritin mutant and the L-ferritin chain, confirming the high specificity...
The journal of physical chemistry. A, Jan 12, 2017
The vibrational exciton (VE) interpretation of intense bisignated couplets in vibrational circula... more The vibrational exciton (VE) interpretation of intense bisignated couplets in vibrational circular dichroism (VCD) spectra of a pair of atropisomeric BODIPY (boron dipyrrin) dimers is discussed. The role of intrinsic magnetic moments is crucial to reproduce the different behaviors of quasi-isomeric BODIPY dimers with different aryl junction.
The journal of physical chemistry letters, 2016
We present a novel mixed method suitable for computing the low-to-middle resolution spectra of sy... more We present a novel mixed method suitable for computing the low-to-middle resolution spectra of systems characterized by a large-amplitude motion s (defined by either a reaction or an internal path) coupled to a bath of harmonic oscillators r, which change with s. The method is based on an adiabatic approximation whereby s is considered much slower than r degrees of freedom and is treated classically. We show that the spectrum can be obtained by a suitable average of quantum vibronic spectra of the fast coordinates computed at representative values of the slow coordinate along the path. By our method we calculate the electronic circular dichroism (ECD) of 2,2,2-trifluoro-anthryl-ethanol, which possesses two conformers with opposite chirality separated by a low-energy barrier. Path-averaged spectra are significantly different from those obtained only at the stable minima: Agreement with experiment is improved. The method represents a generalization of those currently based on harmonic...
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Papers by Giovanna Longhi