Circularly polarized luminescence of natural products lycorine and narciclasine: role of excited-state intramolecular proton-transfer and test of pH sensitivity

Mazzeo, Giuseppe; Fusè, Marco; Evidente, Antonio; Abbate, Sergio; Longhi, Giovanna

doi:10.1039/d3cp02600k

Cited by 6 publications

(2 citation statements)

References 76 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…6•10 −5 . It is also worth noting that the large Stokes shift experienced suggests an excited state intramolecular proton transfer process, which was recently investigated through fluorescence and CPL in natural compounds (Mazzeo et al, 2023).…”

Section: Assignment Of Absolute Configuration Of Germichrysonementioning

confidence: 99%

Neurodegeneration: can metabolites from Eremurus persicus help?

Cavalloro,

Marchesi,

Linciano

et al. 2024

Front. Pharmacol.

Self Cite

View full text Add to dashboard Cite

The number of patients affected by neurodegenerative diseases is increasing worldwide, and no effective treatments have been developed yet. Although precision medicine could represent a powerful tool, it remains a challenge due to the high variability among patients. To identify molecules acting with innovative mechanisms of action, we performed a computational investigation using SAFAN technology, focusing specifically on HuD. This target belongs to the human embryonic lethal abnormal visual-like (ELAV) proteins and plays a key role in neuronal plasticity and differentiation. The results highlighted that the molecule able to bind the selected target was (R)-aloesaponol-III-8-methyl ether [(R)-ASME], a metabolite extracted from Eremurus persicus. Notably, this molecule is a TNF-α inhibitor, a cytokine involved in neuroinflammation. To obtain a suitable amount of (R)-ASME to confirm its activity on HuD, we optimized the extraction procedure. Together with ASME, another related metabolite, germichrysone, was isolated. Both ASME and germichrysone underwent biological investigation, but only ASME confirmed its ability to bind HuD. Given the multifactorial nature of neurodegenerative diseases, we decided to investigate ASME as a proteasome activator, being molecules endowed with this kind of activity potentially able to counteract aggregations of dysregulated proteins. ASME was able to activate the considered target both in enzymatic and cellular assays. Therefore, ASME may be considered a promising hit in the fight against neurodegenerative diseases.

show abstract

Section: Assignment Of Absolute Configuration Of Germichrysonementioning

confidence: 99%

Neurodegeneration: can metabolites from Eremurus persicus help?

Cavalloro,

Marchesi,

Linciano

et al. 2024

Front. Pharmacol.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Therefore, quantitative evaluation of pH changes in environmental and biochemical analyses appears vital in monitoring and understanding these pathological processes, and increasingly in ensuring proper medical diagnosis and treatment evaluation. To date, a number of methods have been developed to measure pH, including electrochemical techniques using electrodes and spectroscopic approaches based on nuclear magnetic resonance (NMR), optical activity, absorption spectroscopy, and fluorescent probes [4][5][6][7]. Recently, extensive efforts have been put into proposing methods to monitor pH changes in situ [8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Acid/Base-Triggered Photophysical and Chiroptical Switching in a Series of Helicenoid Compounds

Guy,

Mosser,

Pitrat

et al. 2023

Molecules

View full text Add to dashboard Cite

A series of molecules that possess two quinolines, benzoquinolines, or phenanthrolines connected in a chiral fashion by a biaryl junction along with their water-soluble derivatives was developed and characterized. The influence of the structure on the basicity of the nitrogen atoms in two heterocycles was examined and the photophysical and chiroptical switching activity of the compounds upon protonation was studied both experimentally and computationally. The results demonstrated that changes in the electronic structure of the protonated vs. neutral species, promoting a bathochromic shift of dominant electronic transitions and alternation of their character from π-to-π* to charge-transfer-type, when additionally accompanied by the high structural flexibility of a system, leading to changes in conformational preferences upon proton binding, produce particularly pronounced modifications of the spectral properties in acidic medium. The latter combined with reversibility of the read-out make some of the molecules in this series very promising multifunctional pH probes.

show abstract

CPL of Mellein and Related Natural Compounds: Analysis of the ESIPT Phenomenon

Mazzeo,

Fusè,

Bloino

et al. 2024

ChemPhysChem

View full text Add to dashboard Cite

(R)‐(‐)‐Mellein, (3R,4R)‐4‐hydroxymellein and (3R,4S)‐4‐hydroxymellein obtained from fungi, i.e. from Diplodia globulosa, were investigated as a class of natural products presenting ESIPT (excited state intramolecular proton transfer) phenomenon, through fluorescence and CPL (circularly polarized luminescence). The study was preceded by the assessment of the absolute configuration through ECD and VCD (electronic and vibrational circular dichroism) spectroscopies in addition to NMR spectra. It is found that ESIPT takes place in these systems very rapidly, and no dual fluorescence has been observed. The experimental study is backed up by TD‐DFT calculations of ECD and CPL spectra, plus MD dynamics to follow proton transfer in the excited state and careful analysis of the puckering dynamics of the lactone ring. Deprotonated forms of the three compounds were also investigated by the same chiroptical experimental and theoretical methods, showing how one can find in natural compounds not only biological activity but also biologically compatible sensing probes.

show abstract

Circularly polarized luminescence of natural products lycorine and narciclasine: role of excited-state intramolecular proton-transfer and test of pH sensitivity

Abstract: Circularly Polarized Luminescence (CPL) is increasingly gaining interest not only for its applicative potentialities but also for understanding the excited state properties of chiral molecules. However, applications of CPL are...

Cited by 6 publications

References 76 publications

Neurodegeneration: can metabolites from Eremurus persicus help?

Neurodegeneration: can metabolites from Eremurus persicus help?

Acid/Base-Triggered Photophysical and Chiroptical Switching in a Series of Helicenoid Compounds

CPL of Mellein and Related Natural Compounds: Analysis of the ESIPT Phenomenon

Contact Info

Product

Resources

About