63 results on '"Fraschetti C"'
Search Results
2. Coriander (Coriandrum sativum) essential oil: effect on multidrug resistant uropathogenic Escherichia coli
- Author
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Scazzocchio, F., Mondì, L., Ammendolia, M. G., Goldoni, P., Comanducci, A., Marazzato, M., Conte, M. P., Federica Rinaldi, Crestoni, M. E., Fraschetti, C., and Longhi, C.
- Subjects
coriandrum sativum ,escherichia coli ,uropathogenic escherichia coli ,essential oil ,antibiotic resistance ,urinary tract infections - Published
- 2017
3. Real time evolution of unprotected protonated galactosamine probed by IRMPD spectroscopy
- Author
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Fraschetti, C., primary, Guarcini, L., additional, Zazza, C., additional, Mannina, L., additional, Circi, S., additional, Piccirillo, S., additional, Chiavarino, B., additional, and Filippi, A., additional
- Published
- 2018
- Full Text
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4. Kinetic enantioselectivity of a protonated bis(diamido)-bridged basket resorcin[4]arene towards alanine peptides
- Author
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Fraschetti, C., primary, Montagna, M., additional, Crestoni, M. E., additional, Calcaterra, A., additional, Aiello, F., additional, Santi, L., additional, and Filippi, A., additional
- Published
- 2017
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5. Protonated pyrimidine nucleosides probed by IRMPD spectroscopy in the memory of Detlef Schroeder
- Author
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Filippi, A, Fraschetti, C, Rondino, F, Piccirillo, S, Steinmetz, V, Guidoni, L, and Speranza, M
- Subjects
Settore CHIM/03 - Chimica Generale e Inorganica - Published
- 2013
6. Spectroscopic evidence for a gas-phase librating G-quartet–Na+ complex
- Author
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Fraschetti, C., primary, Montagna, M., additional, Guarcini, L., additional, Guidoni, L., additional, and Filippi, A., additional
- Published
- 2014
- Full Text
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7. Spectroscopic evidence for a gas-phase librating G-quartet-Na+ complex.
- Author
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Fraschetti, C., Montagna, M., Guarcini, L., Filippi, A., and Guidoni, L.
- Subjects
- *
GIBBS' free energy , *QUADRUPLEX nucleic acids , *MOLECULAR biology , *INFRARED spectroscopy , *GAS phase reactions - Abstract
The IRMPD spectrum of the G-quartet-Na+ complex, in combination with an ab initio molecular dynamic simulation, revealed the presence of two metastable populations of conformers separated by a free energy barrier easily accessible at room temperature. [ABSTRACT FROM AUTHOR]
- Published
- 2014
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8. Gas-phase facial diastereoselectivity of equatorial and axial 4-chloro-adamant-2-yl cations
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Fraschetti, C, Novara, F R, Filippi, A, Speranza, M, Trout, Neil, Adcock, W, Marcantoni, E, Renzi, G, Roselli, G, and Marcolini, M
- Published
- 2009
9. Lentisk ( Pistacia lentiscus ) Oil Nanoemulsions Loaded with Levofloxacin: Phytochemical Profiles and Antibiofilm Activity against Staphylococcus spp.
- Author
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Maurizi L, Lasalvia A, Fabiano MG, D'Intino E, Del Cioppo F, Fraschetti C, Filippi A, Ammendolia MG, Conte AL, Forte J, Corinti D, Crestoni ME, Carafa M, Marianecci C, Rinaldi F, and Longhi C
- Abstract
Most clinical isolates of both Staphylococcus aureus and Staphylococcus epidermidis show the capacity to adhere to abiotic surfaces and to develop biofilms resulting in a contribution to chronic human skin infections. Antibiotic resistance and poor biofilm penetration are the main causes of ineffective therapeutic treatment in killing bacteria within biofilms. A possible strategy could be represented by drug delivery systems, such as nanoemulsions (composed of bioactive oil, surfactant and water phase), which are useful for enhancing the drug permeation of a loaded drug inside the biofilm and its activity. Phytochemical characterization of Pistacia lentiscus oil (LO) by direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) allowed the identification of bioactive compounds with antimicrobial properties, including fatty acids and phenolic compounds. Several monoterpenes and sesquiterpenes have been also detected and confirmed by gas chromatography-mass spectrometric (GC-MS) analysis, together providing a complete metabolomic profiling of LO. In the present study, a nanoemulsion composed of LO has been employed for improving Levofloxacin water solubility. A deep physical-chemical characterization of the nanoemulsion including hydrodynamic diameter, ζ-potential, morphology, entrapment efficiency, stability release and permeation studies was performed. Additionally, the antimicrobial/antibiofilm activity of these preparations was evaluated against reference and clinical Staphylococcus spp. strains. In comparison to the free-form antibiotic, the loaded NE nanocarriers exhibited enhanced antimicrobial activity against the sessile forms of Staphylococcus spp. strains.
- Published
- 2024
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10. Chemical Composition and Anti- Candida Activity of Mentha suaveolens Ehrh. Essential Oils Obtained by Different Distillation Processes.
- Author
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Tadić V, Božović M, Sapienza F, Astolfi R, Mladenović M, Zaka MC, Del Bove F, Borzacchi F, Fraschetti C, Rossi C, Vertuani S, Baldisserotto A, Manfredini S, and Ragno R
- Subjects
- Candida, Limonene, Distillation, Steam, Candida albicans, Oils, Volatile pharmacology, Oils, Volatile chemistry, Mentha chemistry
- Abstract
A comparative study on essential oils extracted from Mentha suaveolens Ehrh. from Italy is reported. Two extraction procedures were investigated: hydrodistillation and steam distillation, carried out as a continuous and fractionated procedure. Fresh and dried plant material from two harvests was used. The hydrodistillation method yielded a higher amount of essential oil. The dried plant was significantly richer in essential oil per kg of starting plant material. Gas chromatography-mass spectrometry analysis of 112 samples showed that the essential oils belong to the piperitenone oxide-rich chemotype. In addition, piperitenone, p-cymen-8-ol, and limonene were among the most abundant compounds in the different samples. A higher amount of piperitenone oxide was obtained by hydrodistillation, while steam distillation gave a higher percentage of piperitenone and limonene. The essential oils were characterized for their anti- Candida albicans activity; higher potency was observed for the samples rich in piperitenone oxide, with MIC values ranging from 0.39 to 0.78 mg·mL
-1 (0.039% and 0.078% p/v). The results of this work provide a deep insight into the methodology of essential oil extraction and the associated chemical variability of M. suaveolens Ehrh. Some of the essential oils are potent against C. albicans and could be considered for potential use in therapy.- Published
- 2023
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11. Effect of Different Soil Treatments on Production and Chemical Composition of Essential Oils Extracted from Foeniculum vulgare Mill., Origanum vulgare L. and Thymus vulgaris L.
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Raffo A, Sapienza FU, Astolfi R, Lombardi G, Fraschetti C, Božović M, Artini M, Papa R, Trecca M, Fiorentino S, Vecchiarelli V, Papalini C, Selan L, and Ragno R
- Abstract
The aim of the study was to investigate how essential oil production and associated chemical composition and related biological activity could be influenced by different cultivation treatments and distillation methods. Foeniculum vulgare Mill. (fennel), Origanum vulgare L. (oregano) and Thymus vulgaris L. (thyme) were cultivated in absence of any fertilizer (control) and in presence of three different fertilizers: a chemical one with augmented mineral phosphorus and potassium, a second added with hydrolyzed organic substance and mineral phosphorus and potassium (organic-mineral) and a third one treated with a high content of organic nitrogen of protein origin (organic). The plants were subjected to steam distillation using two modalities, recycled and continuous, to obtain 32 essential oil samples. Chemical composition analysis was performed using gas chromatography-mass spectrometry; in vitro antimicrobial activity was evaluated using a broth microdilution method. In general, the recycled distillation method appeared to have a slightly higher yield than the continuous method. The "mineral" and "organic-mineral" treatments resulted in a higher yield compared to the "organic" or "control" treatments, and this was particularly evident in the recycled method. The "control" plants had a lower yield of essential oils. Anethole (13.9-59.5%) and estragole (13.4-52.2%) were the main constituents of the fennel oils; p -cymene and its derivatives carvacrol and thymol were the main constituents of the oregano and thyme samples. The antimicrobial activity of the thyme oils on Staphylococcus aureus ranged from 0.31 to 0.16% ( v/v ); a lower effect of the oregano samples and no activity of the fennel samples were observed. The essential oils failed to inhibit the growth of Pseudomonas aeruginosa strains.
- Published
- 2023
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12. First-in-Class Selective Inhibitors of the Lysine Acetyltransferase KAT8.
- Author
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Fiorentino F, Sementilli S, Menna M, Turrisi F, Tomassi S, Pellegrini FR, Iuzzolino A, D'Acunzo F, Feoli A, Wapenaar H, Taraglio S, Fraschetti C, Del Bufalo D, Sbardella G, Dekker FJ, Paiardini A, Trisciuoglio D, Mai A, and Rotili D
- Subjects
- Humans, Histones metabolism, Acetylation, Histone Acetyltransferases metabolism, Lysine Acetyltransferases metabolism, Carcinoma, Non-Small-Cell Lung drug therapy, Lung Neoplasms, Leukemia, Myeloid, Acute
- Abstract
KAT8 is a lysine acetyltransferase primarily catalyzing the acetylation of Lys16 of histone H4 (H4K16). KAT8 dysregulation is linked to the development and metastatization of many cancer types, including non-small cell lung cancer (NSCLC) and acute myeloid leukemia (AML). Few KAT8 inhibitors have been reported so far, none of which displaying selective activity. Based on the KAT3B/KDAC inhibitor C646, we developed a series of N -phenyl-5-pyrazolone derivatives and identified compounds 19 and 34 as low-micromolar KAT8 inhibitors selective over a panel of KATs and KDACs. Western blot, immunofluorescence, and CETSA experiments demonstrated that both inhibitors selectively target KAT8 in cells. Moreover, 19 and 34 exhibited mid-micromolar antiproliferative activity in different cancer cell lines, including NSCLC and AML, without impacting the viability of nontransformed cells. Overall, these compounds are valuable tools for elucidating KAT8 biology, and their simple structures make them promising candidates for future optimization studies.
- Published
- 2023
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13. Pomegranate Fruit Cracking during Maturation: From Waste to Valuable Fruits.
- Author
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Fraschetti C, Goci E, Nicolescu A, Cairone F, Carradori S, Filippi A, Palmieri V, Mocan A, and Cesa S
- Abstract
The pomegranate is an emerging functional food which is nowadays becoming more and more commercially attractive. Each part of this fruit (peels, arils and seeds) has a specific phytocomplex, rich in anti-oxidant and anti-radical compounds. Among these, punicalagin and ellagic acid continue to be widely studied for their numerous beneficial effects on human health (anti-inflammatory effects, anti-diabetes activity, cardio-protection, cancer prevention). Despite their exceptionally valuable composition and high adaptability to different climatic conditions, pomegranate fruits are highly susceptible to splitting during different stages of ripening, so much so that an estimated 65% of the production may be lost. A "zero-kilometer" approach should therefore be adopted to utilize such a valuable product otherwise destined to be downgraded or even incinerated, with a very high environmental impact. The aim of this work is to highlight and compare the compositional differences between whole and split pomegranates belonging to the cultivar Dente di Cavallo, grown in Apulia (Italy), to assess a valuable role for this split fruit usually considered as waste. The arils and peels are subjected to extraction procedures and the extracts analyzed by CIEL*a*b*, HPLC-DAD and HS-SPME/GC-MS. Moreover, an assessment of the inhibitory activity against α-glucosidase, acetylcholinesterase and tyrosinase enzymes has also been applied. The data show a better chemical profile in split fruits (namely 60% more anthocyanin content than intact fruit) with very interesting results in terms of α-glucosidase inhibition. The juices obtained by squeezing are also compared to commercial juices ("Salus Melagrana" and "La Marianna") processed from the same cultivar and subjected to the same protocol analysis.
- Published
- 2023
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14. Effects of Processing on Chemical Composition of Extracts from Sour Cherry Fruits, a Neglected Functional Food.
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Cairone F, Fraschetti C, Menghini L, Zengin G, Filippi A, Casadei MA, and Cesa S
- Abstract
Sour cherries fruits ( Prunus cerasus L., syn P. cerasus var. austera ) are locally known as "visciola di Sezze", due to the name of the city where they are traditionally cultivated in Lazio Region, Italy. Fruit samples from three harvesting years (June 2019, 2020 and 2021), were submitted to a protocol of analyses to detect the bioactive content based on year of harvest, freezing, homogenization and thermic treatments. Polyphenolic components, particularly anthocyanin compounds, were extracted, purified and analyzed by HPLC-DAD and DI-ESI-MS. An anthocyanin content between 0.24 and 21 mg/g fresh weight and a flavonols content between 0.04 and 0.2 mg/g fresh weight were found, depending on the harvest year and the applied procedures. Anthocyanins, besides being the principal components, were mainly represented by cyanidin-3-glucosyl-rutinoside (about 80%), a not particularly widespread molecule, mostly accounting for polyphenolic content. Color analysis and anti-radical activity of the different obtained extracts were performed with the aim to correlate organoleptic characters and health potential to the detected anthocyanins and flavanols content. Results show that immediate post-harvest freezing is the best way to preserve the bioactive content, the correlated color expression and anti-radical activity.
- Published
- 2023
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15. Theoretical-Computational Modeling of Gas-State Thermodynamics in Flexible Molecular Systems: Ionic Liquids in the Gas Phase as a Case Study.
- Author
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Amadei A, Ciccioli A, Filippi A, Fraschetti C, and Aschi M
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- Reproducibility of Results, Thermodynamics, Gases, Molecular Dynamics Simulation, Ionic Liquids
- Abstract
A theoretical-computational procedure based on the quasi-Gaussian entropy (QGE) theory and molecular dynamics (MD) simulations is proposed for the calculation of thermodynamic properties for molecular and supra-molecular species in the gas phase. The peculiarity of the methodology reported in this study is its ability to construct an analytical model of all the most relevant thermodynamic properties, even within a wide temperature range, based on a practically automatic sampling of the entire conformational repertoire of highly flexible systems, thereby bypassing the need for an explicit search for all possible conformers/rotamers deemed relevant. In this respect, the reliability of the presented method mainly depends on the quality of the force field used in the MD simulations and on the ability to discriminate in a physically coherent way between semi-classical and quantum degrees of freedom. The method was tested on six model systems (n-butane, n-butane, n-octanol, octadecane, 1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic pairs), which, being experimentally characterized and already addressed by other theoretical-computational methods, were considered as particularly suitable to allow us to evaluate the method's accuracy and efficiency, bringing out advantages and possible drawbacks. The results demonstrate that such a physically coherent yet relatively simple method can represent a further valid computational tool that is alternative and complementary to other extremely efficient computational methods, as it is particularly suited for addressing the thermodynamics of gaseous systems with a high conformational complexity over a large range of temperature.
- Published
- 2022
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16. Anti-Inflammatory and Antioxidant Effects Induced by Allium sativum L. Extracts on an Ex Vivo Experimental Model of Ulcerative Colitis.
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Recinella L, Gorica E, Chiavaroli A, Fraschetti C, Filippi A, Cesa S, Cairone F, Martelli A, Calderone V, Veschi S, Lanuti P, Cama A, Orlando G, Ferrante C, Menghini L, Di Simone SC, Acquaviva A, Libero ML, Nilofar, Brunetti L, and Leone S
- Abstract
Inflammatory bowel diseases (IBDs) are chronic and multifactorial inflammatory conditions of the colonic mucosa (ulcerative colitis), characterized by increased and unbalanced immune response to external stimuli. Garlic and its bioactive constituents were reported to exert various biological effects, including anti-inflammatory, antioxidant and immunomodulatory activities. We aimed to evaluate the protective effects of a hydroalcoholic (GHE) and a water (GWE) extract from a Sicilian variety of garlic, known as Nubia red garlic, on an ex vivo experimental model of ulcerative colitis, involving isolated LPS-treated mouse colon specimens. Both extracts were able to counteract LPS-induced cyclooxygenase (COX)-2, tumor necrosis factor (TNF)-α, nuclear factor-kB (NF-kB), and interleukin (IL)-6 gene expression in mouse colon. Moreover, the same extracts inhibited prostaglandin (PG)E
2 , 8-iso-PGF2α , and increased the 5-hydroxyindoleacetic acid/serotonin ratio following treatment with LPS. In particular, GHE showed a better anti-inflammatory profile. The anti-inflammatory and antioxidant effects induced by both extracts could be related, at least partially, to their polyphenolic composition, with particular regards to catechin. Concluding, our results showed that GHE and GWE exhibited protective effects in colon, thus suggesting their potential use in the prevention and management of ulcerative colitis.- Published
- 2022
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17. Role of Caryophyllane Sesquiterpenes in the Entourage Effect of Felina 32 Hemp Inflorescence Phytocomplex in Triple Negative MDA-MB-468 Breast Cancer Cells.
- Author
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Di Giacomo S, Mariano A, Gullì M, Fraschetti C, Vitalone A, Filippi A, Mannina L, Scotto d'Abusco A, and Di Sotto A
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- Antineoplastic Agents, Phytogenic chemistry, Cannabis chemistry, Cell Line, Tumor, Dose-Response Relationship, Drug, Drug Synergism, Humans, Monocyclic Sesquiterpenes chemistry, Monocyclic Sesquiterpenes pharmacology, Phytochemicals chemistry, Plant Extracts chemistry, Polycyclic Sesquiterpenes chemistry, Receptor, Cannabinoid, CB2 metabolism, Triple Negative Breast Neoplasms, Antineoplastic Agents, Phytogenic pharmacology, Inflorescence chemistry, Phytochemicals pharmacology, Plant Extracts pharmacology, Polycyclic Sesquiterpenes pharmacology
- Abstract
Cannabis sativa L. crops have been traditionally exploited as sources of fibers, nutrients, and bioactive phytochemicals of medical interest. In the present study, two terpene-rich organic extracts, namely FOJ and FOS, obtained from Felina 32 hemp inflorescences collected in June and September, respectively, have been studied for their in vitro anticancer properties. Particularly, their cytotoxicity was evaluated in different cancer cell lines, and the possible entourage effect between nonintoxicating phytocannabinoids (cannabidiol and cannabichromene) and caryophyllane sesquiterpenes (β-caryophyllene, β-caryophyllene oxide and α-humulene), as identified at GC/MS analysis, was characterized. Modulation of cannabinoid CB1 and CB2 receptors was studied as a mechanistic hypothesis. Results highlighted marked cytotoxic effects of FOJ, FOS, and pure compounds in triple negative breast cancer MDA-MB-468 cells, likely mediated by a CB2 receptor activation. Cannabidiol was the main cytotoxic constituent, although low levels of caryophyllane sesquiterpenes and cannabichromene induced potentiating effects; the presence in the extracts of unknown antagonistic compounds has been highlighted too. These results suggest an interest in Felina 32 hemp inflorescences as a source of bioactive phytocomplexes with anticancer properties and strengthen the importance of considering the possible involvement of minor terpenes, such as caryophyllane sesquiterpenes, in the entourage effect of hemp-based extracts.
- Published
- 2021
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18. Evaluation of a new portable 1-lead digital cardiac monitor (eKuore) compared with standard base-apex electrocardiography in healthy horses.
- Author
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Vitale V, Vezzosi T, Tognetti R, Fraschetti C, and Sgorbini M
- Subjects
- Animals, Artifacts, Electrodes, Heart Rate physiology, Smartphone, Electrocardiography veterinary, Heart physiology, Horses physiology
- Abstract
Recently, the use of smartphone ECG devices has been reported in humans and animals. Nevertheless, as the electrodes of these devices are inseparable, they can create only a precordial reading in veterinary species. Thus, although the smartphone ECG devices are considered valuable as a screening tool for the detection of some common arrhythmias, they are not always a reliable method for the measurement of the duration of the electrical deflections. The objectives of this study were to evaluate the feasibility of a novel smartphone ECG device, to report the readings obtained recorded simultaneously with a reference ECG system, and to compare the heart rate and duration of cardiac deflections obtained with the two methods. A total of 28 healthy mares of different breeds and age were included in this study and ECG recordings were obtained simultaneously with a reference ECG telemetry system with surface electrodes attached to the skin with alligator clips using a standard base-apex system and a smartphone ECG device with electrodes positioned alternatively with a standard and a modified base apex derivation. All the recordings obtained were considered acceptable for interpretation. An excellent agreement was found between the two methods for the evaluation of heart rate and polarity of cardiac deflections. No differences regarding number, duration and percentage of artifacts were found. This technology could become a valid diagnostic tool in the cardiological assessment of horses, in particular on the field., Competing Interests: The authors have declared that no competing interests exist.
- Published
- 2021
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19. Protective Effects Induced by a Hydroalcoholic Allium sativum Extract in Isolated Mouse Heart.
- Author
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Recinella L, Chiavaroli A, Masciulli F, Fraschetti C, Filippi A, Cesa S, Cairone F, Gorica E, De Leo M, Braca A, Martelli A, Calderone V, Orlando G, Ferrante C, Menghini L, Di Simone SC, Veschi S, Cama A, Brunetti L, and Leone S
- Subjects
- Animals, Antioxidants pharmacology, Gas Chromatography-Mass Spectrometry, Mice, Solid Phase Microextraction, Cardiotonic Agents pharmacology, Garlic chemistry, Heart drug effects, Oxidative Stress drug effects, Plant Extracts pharmacology
- Abstract
The aim of the present study was to investigate the possible protective effects of a garlic hydroalcoholic extract on the burden of oxidative stress and inflammation occurring on mouse heart specimens exposed to E. coli lipopolysaccharide (LPS), which is a well-established inflammatory stimulus. Headspace solid-phase microextraction combined with the gas chromatography-mass spectrometry (HS-SPME/GC-MS) technique was applied to determine the volatile fraction of the garlic powder, and the HS-SPME conditions were optimized for each of the most representative classes of compounds. CIEL*a*b* colorimetric analyses were performed on the powder sample at the time of delivery, after four and after eight months of storage at room temperature in the dark, to evaluate the color changing. Freshly prepared hydroalcoholic extract was also evaluated in its color character. Furthermore, the hydroalcoholic extract was analyzed through GC-MS. The extract was found to be able to significantly inhibit LPS-induced prostaglandin (PG) E
2 and 8-iso-PGF2α levels, as well as mRNA levels of cyclooxygenase (COX)-2, interleukin (IL)-6, and nuclear factor-kB (NF-kB), in heart specimens. Concluding, our findings showed that the garlic hydroalcoholic extract exhibited cardioprotective effects on multiple inflammatory and oxidative stress pathways.- Published
- 2021
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20. Unprotected Galactosamine as a Dynamic Key for a Cyclochiral Lock.
- Author
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Fraschetti C, Letzel MC, Paletta M, Mattay J, Crestoni ME, Chiavarino B, and Filippi A
- Abstract
The discrimination of d-galactosamine ( G ), representative of the amino-sugar class of compounds, has been probed through nano-ESI-FT-ICR mass spectrometry by isolating the relevant [ C ·H· G ]
+ proton-bound complexes with the enantiomers of the cyclochiral resorcin[4]arene C and allowing them to react toward three primary amines ( B = EtNH2 , i PrNH2 , and ( R )- and ( S )- s BuNH2 ). The system under investigation presents several features that help to unveil the behavior of unprotected G in such a supramolecular architecture: (i) the hydrophobic derivatization of the C convex side forces the polar guest G to be coordinated by the cyclochiral concave region; (ii) protonated d-galactosamine exists as an anomeric mixture, dynamically interconverting throughout the experimental time-window; and (iii) different basicities of B allow the experiment to subtly tune the reactivity of the [ C ·H· G ]+ complexes. Three [ C ·H· G ]+ aggregate-types were found to exist, differing in both their origin and reactivity. The most reactive adducts ([ C ·H· G ]ESI + ), generated in the electrospray environment, undergo a G -to- B ligand exchange in competition with a partial isomerization to the unreactive [ C ·H· G ]GAS + -type complexes. Finally, the poorly reactive [ C ·H· G ]SOL + aggregates are formed in solution over an hours-long time scale. A cyclochirality effect on the reactivity was found to depend on the considered [ C ·H· G ]+ aggregate-type.- Published
- 2021
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21. Chemical and Bioinformatics Analyses of the Anti-Leishmanial and Anti-Oxidant Activities of Hemp Essential Oil.
- Author
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Menghini L, Ferrante C, Carradori S, D'Antonio M, Orlando G, Cairone F, Cesa S, Filippi A, Fraschetti C, Zengin G, Ak G, Tacchini M, and Iqbal K
- Subjects
- Animals, Gas Chromatography-Mass Spectrometry, Mice, Antioxidants pharmacology, Antiprotozoal Agents pharmacology, Cannabis chemistry, Computational Biology, Leishmania drug effects, Oils, Volatile pharmacology, Plant Extracts pharmacology
- Abstract
Industrial hemp is a multiuse crop that has been widely cultivated to produce fibers and nutrients. The capability of the essential oil (EO) from inflorescences as antimicrobial agent has been reported. However, literature data are still lacking about the hemp EO antiprotozoal efficacy in vivo. The present study aims to unravel this concern through the evaluation of the efficacy of hemp EOs (2.5 mL/kg, intraperitoneally) of three different cultivars, namely Futura 75 , Carmagnola selezionata and Eletta campana , in mice intraperitoneally infected with Leishmania tropica . A detailed description of EO composition and targets-components analysis is reported. Myrcene, α-pinene and E -caryophyllene were the main components of the EOs, as indicated by the gas-chromatographic analysis. However, a prominent position in the scenario of the theoretical interactions underlying the bio-pharmacological activity was also occupied by selina-3,7(11)-diene, which displayed affinities in the micromolar range (5.4-28.9) towards proliferator-activated receptor α, cannabinoid CB2 receptor and acetylcholinesterase. The content of this compound was higher in Futura 75 and Eletta campana , in accordance with their higher scavenging/reducing properties and efficacy against the tissue wound, induced by L. tropica . Overall, the present study recommends hemp female inflorescences, as sources of biomolecules with potential pharmacological applications, especially towards infective diseases.
- Published
- 2021
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22. Binding Motifs in the Naked Complexes of Target Amino Acids with an Excerpt of Antitumor Active Biomolecule: An Ion Vibrational Spectroscopy Assay.
- Author
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Chiavarino B, Sinha RK, Crestoni ME, Corinti D, Filippi A, Fraschetti C, Scuderi D, Maitre P, and Fornarini S
- Subjects
- Hydrogen Bonding, Photons, Protons, Vibration, Amino Acids chemistry, Antineoplastic Agents chemistry, Spectrophotometry, Infrared
- Abstract
The structures of proton-bound complexes of 5,7-dimethoxy-4H-chromen-4-one (1) and basic amino acids (AAs), namely, histidine (His) and lysine (Lys), have been examined by means of mass spectrometry coupled with IR ion spectroscopy and quantum chemical calculations. This selection of systems is based on the fact that 1 represents a portion of glabrescione B, a natural small molecule of promising antitumor activity, while His and Lys are protein residues lining the cavity of the alleged receptor binding site. These species are thus a model of the bioactive adduct, although clearly the isolated state of the present study bears little resemblance to the complex biological environment. A common feature of [1+AA+H]
+ complexes is the presence of a protonated AA bound to neutral 1, in spite of the fact that the gas-phase basicity of 1 is comparable to those of Lys and His. The carbonyl group of 1 acts as a powerful hydrogen-bond acceptor. Within [1+AA+H]+ the side-chain substituents (imidazole group for His and terminal amino group for Lys) present comparable basic properties to those of the α-amino group, taking part to a cooperative hydrogen-bond network. Structural assignment, relying on the comparative analysis of the infrared multiple photon dissociation (IRMPD) spectrum and calculated IR spectra for the candidate geometries, derives from an examination over two frequency ranges: 900-1800 and 2900-3700 cm-1 . Information gained from the latter one proved especially valuable, for example, pointing to the contribution of species characterized by an unperturbed carboxylic OH or imidazole NH stretching mode., (© 2020 Wiley-VCH GmbH.)- Published
- 2021
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23. Molecular Properties of Bare and Microhydrated Vitamin B5-Calcium Complexes.
- Author
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Corinti D, Chiavarino B, Scuderi D, Fraschetti C, Filippi A, Fornarini S, and Crestoni ME
- Subjects
- Gases chemistry, Photons, Quantum Theory, Spectrophotometry, Infrared, Calcium chemistry, Pantothenic Acid chemistry
- Abstract
Pantothenic acid, also called vitamin B5, is an essential nutrient involved in several metabolic pathways. It shows a characteristic preference for interacting with Ca(II) ions, which are abundant in the extracellular media and act as secondary mediators in the activation of numerous biological functions. The bare deprotonated form of pantothenic acid, [panto-H]
- , its complex with Ca(II) ion, [Ca(panto-H)]+ , and singly charged micro-hydrated calcium pantothenate [Ca(panto-H)(H2 O)]+ adduct have been obtained in the gas phase by electrospray ionization and assayed by mass spectrometry and IR multiple photon dissociation spectroscopy in the fingerprint spectral range. Quantum chemical calculations at the B3LYP(-D3) and MP2 levels of theory were performed to simulate geometries, thermochemical data, and linear absorption spectra of low-lying isomers, allowing us to assign the experimental absorptions to particular structural motifs. Pantothenate was found to exist in the gas phase as a single isomeric form showing deprotonation on the carboxylic moiety. On the contrary, free and monohydrated calcium complexes of deprotonated pantothenic acid both present at least two isomers participating in the gas-phase population, sharing the deprotonation of pantothenate on the carboxylic group and either a fourfold or fivefold coordination with calcium, thus justifying the strong affinity of pantothenate for the metal.- Published
- 2021
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24. Chemico-Biological Characterization of Torpedino Di Fondi ® Tomato Fruits: A Comparison with San Marzano Cultivar at Two Ripeness Stages.
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Ingallina C, Maccelli A, Spano M, Di Matteo G, Di Sotto A, Giusti AM, Vinci G, Di Giacomo S, Rapa M, Ciano S, Fraschetti C, Filippi A, Simonetti G, Cordeiro C, Silva MS, Crestoni ME, Sobolev AP, Fornarini S, and Mannina L
- Abstract
Torpedino di Fondi (TF) is a hybrid tomato landrace developed in Sicily and recently introduced in the south Lazio area along with the classical San Marzano (SM) cultivar. The present study aimed at characterizing TF tomatoes at both pink and red ripening stages, and at comparing them with traditional SM tomatoes. A multidisciplinary approach consisting of morphological, chemical (FT-ICR MS, NMR, HPLC, and spectrophotometric methods), and biological (antioxidant and antifungal in vitro activity) analyses was applied. Morphological analysis confirmed the mini-San Marzano nature and the peculiar crunchy and solid consistency of TF fruits. Pink TF tomatoes displayed the highest content of hydrophilic antioxidants, like total polyphenols (0.192 mg/g), tannins (0.013 mg/g), flavonoids (0.204 mg/g), and chlorophylls a (0.344 mg/g) and b (0.161 mg/g), whereas red TF fruits were characterized by the highest levels of fructose (3000 mg/100 g), glucose (2000 mg/100 g), tryptophan (2.7 mg/100 g), phenylalanine (13 mg/100 g), alanine (25 mg/100 g), and total tri-unsaturated fatty acids (13% mol). Red SM fruits revealed the greatest content of lipophilic antioxidants, with 1234 mg/g of total carotenoids. In agreement with phenolics content, TF cultivar showed the greatest antioxidant activity. Lastly, red TF inhibited Candida species ( albicans , glabrata and krusei ) growth.
- Published
- 2020
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25. Cannabis sativa L. Inflorescences from Monoecious Cultivars Grown in Central Italy: An Untargeted Chemical Characterization from Early Flowering to Ripening.
- Author
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Ingallina C, Sobolev AP, Circi S, Spano M, Fraschetti C, Filippi A, Di Sotto A, Di Giacomo S, Mazzoccanti G, Gasparrini F, Quaglio D, Campiglia E, Carradori S, Locatelli M, Vinci G, Rapa M, Ciano S, Giusti AM, Botta B, Ghirga F, Capitani D, and Mannina L
- Subjects
- Cannabinoids chemistry, Chromatography, High Pressure Liquid, Flavonoids chemistry, Flowers chemistry, Gas Chromatography-Mass Spectrometry, Italy, Magnetic Resonance Spectroscopy, Molecular Structure, Plant Development, Cannabis chemistry, Cannabis growth & development, Inflorescence chemistry
- Abstract
The chemical composition of the inflorescences from four Cannabis sativa L. monoecious cultivars (Ferimon, Uso-31, Felina 32 and Fedora 17), recently introduced in the Lazio Region, was monitored over the season from June to September giving indications on their sensorial, pharmaceutical/nutraceutical proprieties. Both untargeted (NMR) and targeted (GC/MS, UHPLC, HPLC-PDA/FD and spectrophotometry) analyses were carried out to identify and quantify compounds of different classes (sugars, organic acids, amino acids, cannabinoids, terpenoids, phenols, tannins, flavonoids and biogenic amines). All cultivars in each harvesting period showed a THC content below the Italian legal limit, although in general THC content increased over the season. Citric acid, malic acid and glucose showed the highest content in the late flowering period, whereas the content of proline drastically decreased after June in all cultivars. Neophytadiene, nerolidol and chlorogenic acid were quantified only in Felina 32 cultivar, characterized also by a very high content of flavonoids, whereas alloaromadendrene and trans -cinnamic acid were detected only in Uso-31 cultivar. Naringenin and naringin were present only in Fedora 17 and Ferimon cultivars, respectively. Moreover, Ferimon had the highest concentration of biogenic amines, especially in July and August. Cadaverine was present in all cultivars but only in September. These results suggest that the chemical composition of Cannabis sativa L. inflorescences depends on the cultivar and on the harvesting period. Producers can use this information as a guide to obtain inflorescences with peculiar chemical characteristics according to the specific use.
- Published
- 2020
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26. Phytochemical and biological characterization of Italian "sedano bianco di Sperlonga" Protected Geographical Indication celery ecotype: A multimethodological approach.
- Author
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Ingallina C, Capitani D, Mannina L, Carradori S, Locatelli M, Di Sotto A, Di Giacomo S, Toniolo C, Pasqua G, Valletta A, Simonetti G, Parroni A, Beccaccioli M, Vinci G, Rapa M, Giusti AM, Fraschetti C, Filippi A, Maccelli A, Crestoni ME, Fornarini S, and Sobolev AP
- Subjects
- Apium metabolism, Biogenic Amines analysis, Chromatography, High Pressure Liquid, Ecotype, Flavonoids analysis, Mycotoxins analysis, Phenols analysis, Plant Extracts chemistry, Plant Leaves chemistry, Plant Leaves metabolism, Apium chemistry, Phytochemicals analysis
- Abstract
Celery is a widely used vegetable known for its peculiar sensorial and nutritional properties. Here, the white celery (Apium graveolens L.) "sedano bianco di Sperlonga" PGI ecotype was investigated to obtain the metabolic profile of its edible parts (blade leaves and petioles) also related to quality, freshness and biological properties. A multi-methodological approach, including NMR, MS, HPLC-PDA, GC-MS and spectrophotometric analyses, was proposed to analyse celery extracts. Sugars, polyalcohols, amino acids, organic acids, phenols, sterols, fatty acids, phthalides, chlorophylls, tannins and flavonoids were detected in different concentrations in blade leaf and petiole extracts, indicating celery parts as nutraceutical sources. The presence of some phenols in celery extracts was here reported for the first time. Low contents of biogenic amines and mycotoxins confirmed celery quality and freshness. Regarding the biological properties, ethanolic celery extracts inhibited the oxidative-mediated DNA damage induced by tert-butylhydroperoxide and scavenged DPPH and ABTS radicals., (Copyright © 2019 Elsevier Ltd. All rights reserved.)
- Published
- 2020
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27. Satureja montana L. Essential Oils: Chemical Profiles/Phytochemical Screening, Antimicrobial Activity and O/W NanoEmulsion Formulations.
- Author
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Maccelli A, Vitanza L, Imbriano A, Fraschetti C, Filippi A, Goldoni P, Maurizi L, Ammendolia MG, Crestoni ME, Fornarini S, Menghini L, Carafa M, Marianecci C, Longhi C, and Rinaldi F
- Abstract
Chemical fingerprints of four different Satureja montana L. essential oils (SEOs) were assayed by an untargeted metabolomics approach based on Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry (MS) coupled with either electrospray ionization or atmospheric pressure chemical ionization ion sources. Analysis and relative quantification of the non-polar volatile fraction were conducted by gas chromatography (GC) coupled to MS. FT-ICR MS confirmed significant differences in the polar metabolite composition, while GC-MS analyses confirmed slight fluctuations in the relative amount of major terpenes and terpenoids, known to play a key role in antimicrobial mechanisms. Oil in eater (O/W) nanoemulsions (NEs) composed by SEOs and Tween 20 or Tween 80 were prepared and analyzed in terms of hydrodynamic diameter, ζ-potential and polydispersity index. The results confirm the formation of stable NEs homogeneous in size. Minimum inhibitory and minimum bactericidal concentrations of SEOs were determined towards Gram-positive ( Listeria monocytogenes , Staphylococcus aureus , Staphylococcus haemolyticus ) and Gram-negative clinical isolates ( Escherichia coli , Klebsiella pneumoniae , Pseudomonas aeruginosa, and Serratia marcescens ). Commercial SEO showed strongest antibacterial activity, while SEO 3 was found to be the most active among the lab made extractions. MIC and MBC values ranged from 0.39 to 6.25 mg·mL
- 1 . Furthermore, a SEO structured in NEs formulation was able to preserve and improve antimicrobial activity., Competing Interests: The authors declare no conflict of interest.- Published
- 2019
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28. Satureja montana L. essential oil and its antimicrobial activity alone or in combination with gentamicin.
- Author
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Vitanza L, Maccelli A, Marazzato M, Scazzocchio F, Comanducci A, Fornarini S, Crestoni ME, Filippi A, Fraschetti C, Rinaldi F, Aleandri M, Goldoni P, Conte MP, Ammendolia MG, and Longhi C
- Subjects
- Biofilms drug effects, Cell Line, Cell Survival drug effects, Cymenes, Drug Combinations, Drug Synergism, Gas Chromatography-Mass Spectrometry, Gram-Negative Bacteria cytology, Gram-Negative Bacteria drug effects, Gram-Positive Bacteria cytology, Gram-Positive Bacteria drug effects, Humans, Microbial Sensitivity Tests, Monoterpenes isolation & purification, Monoterpenes pharmacology, Oils, Volatile chemistry, Plant Oils chemistry, Thymol isolation & purification, Thymol pharmacology, Anti-Infective Agents pharmacology, Gentamicins pharmacology, Oils, Volatile pharmacology, Plant Extracts pharmacology, Plant Oils pharmacology, Satureja chemistry
- Abstract
Many essential oils (EOs) are screened as potential sources of antimicrobial compounds. EOs from the genus Satureja have recognized biological properties, including analgesic, anti-inflammatory, immunomodulatory, anticancer, and antimicrobial activity. This study aimed to obtain a metabolite profile of commercial essential oil of S. montana L. (SEO) and to evaluate its antimicrobial properties, both alone and combined with gentamicin towards Gram-negative and Gram-positive bacterial strains. Untargeted analyses based on direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and on GC-MS have provided a high metabolome coverage, allowing to identify carvacrol, cymene and thymol as the major components of commercial SEO. SEO exerted an antimicrobial activity and induced a synergistic interaction with gentamicin against both reference and clinical bacterial strains. A significant reduction of Escherichia coli, Staphylococcus aureus and Listeria monocytogenes biofilm formation was induced by SEO. As a result of SEO treatment, clear morphological bacterial alterations were visualized by scanning electron microscopy: L. monocytogenes and S. aureus showed malformed cell surface or broken cells with pores formation, whereas E. coli displayed collapsed cell surface. These results encourage further studies about bactericidal and antibiotic synergistic effect of SEO for combined therapy in clinical setting as well as in agricultural systems., (Copyright © 2018 Elsevier Ltd. All rights reserved.)
- Published
- 2019
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29. Chromatographic Analyses, In Vitro Biological Activities, and Cytotoxicity of Cannabis sativa L. Essential Oil: A Multidisciplinary Study.
- Author
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Zengin G, Menghini L, Di Sotto A, Mancinelli R, Sisto F, Carradori S, Cesa S, Fraschetti C, Filippi A, Angiolella L, Locatelli M, Mannina L, Ingallina C, Puca V, D'Antonio M, and Grande R
- Subjects
- Anti-Bacterial Agents chemistry, Anti-Bacterial Agents pharmacology, Antineoplastic Agents, Phytogenic chemistry, Antineoplastic Agents, Phytogenic pharmacology, Antioxidants chemistry, Antioxidants pharmacology, Bacteria drug effects, Caco-2 Cells, Cell Line, Tumor, Ethnopharmacology, Humans, Italy, MCF-7 Cells, Microbial Sensitivity Tests, Oils, Volatile pharmacology, Phenols chemistry, Phenols pharmacology, Plankton drug effects, Cannabis chemistry, Flavonoids chemistry, Flavonoids pharmacology, Oils, Volatile analysis
- Abstract
Due to renewed interest in the cultivation and production of Italian Cannabis sativa L., we proposed a multi-methodological approach to explore chemically and biologically both the essential oil and the aromatic water of this plant. We reported the chemical composition in terms of cannabinoid content, volatile component, phenolic and flavonoid pattern, and color characteristics. Then, we demonstrated the ethnopharmacological relevance of this plant cultivated in Italy as a source of antioxidant compounds toward a large panel of enzymes (pancreatic lipase, α-amylase, α-glucosidase, and cholinesterases) and selected clinically relevant, multidrug-sensible, and multidrug-resistant microbial strains ( Staphylococcus aureus , Helicobacter pylori , Candida , and Malassezia spp.), evaluating the cytotoxic effects against normal and malignant cell lines. Preliminary in vivo cytotoxicity was also performed on Galleria mellonella larvae. The results corroborate the use of this natural product as a rich source of important biologically active molecules with particular emphasis on the role exerted by naringenin, one of the most important secondary metabolites.
- Published
- 2018
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30. Spectroscopic Discrimination of Diastereomeric Complexes Involving an Axially Chiral Receptor.
- Author
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Filippi A, Fraschetti C, Guarcini L, Zazza C, Ema T, and Speranza M
- Abstract
The infrared multiphoton dissociation (IRMPD) spectra of electrospray ionization (ESI)-formed proton-bound complexes between the axially chiral multifunctional macrocycle M
aR and d- and l-phenylalanine (PD and PL ) or d- and l-3,4-dihydroxyphenylalanine (DD and DL ) are recorded in the ν˜ =2800-3700 cm-1 region. Whereas the diastereomeric [MaR ⋅H⋅PD ]+ and [MaR ⋅H⋅PL ]+ complexes do not show any significant spectral differences, the spectrum of [MaR ⋅H⋅DD ]+ clearly diverges from that of its [MaR ⋅H⋅DL ]+ diastereomer. A comparison of the experimental spectra with the B3LYP/6-31G**-calculated harmonic vibrational frequencies of a number of stable structures indicates the formation, in the ESI source, of very similar spectroscopically active structures, with the protonated amino acid placed outside the flat cavity of the macrocycle and hydrogen-bonded at its O2 center. Different spectral signatures of the [MaR ⋅H⋅DD ]+ and [MaR ⋅H⋅DL ]+ complexes are attributed to the coexistence of several stable rotamers in the ESI source., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2017
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31. Coriander (Coriandrum sativum) Essential Oil: Effect on Multidrug Resistant Uropathogenic Escherichia coli.
- Author
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Scazzocchio F, Mondì L, Ammendolia MG, Goldoni P, Comanducci A, Marazzato M, Conte MP, Rinaldi F, Crestoni ME, Fraschetti C, and Longhi C
- Subjects
- Anti-Bacterial Agents chemistry, Drug Resistance, Multiple, Bacterial, Escherichia coli Infections microbiology, Humans, Microbial Sensitivity Tests, Oils, Volatile chemistry, Uropathogenic Escherichia coli growth & development, Anti-Bacterial Agents pharmacology, Coriandrum chemistry, Oils, Volatile pharmacology, Plant Oils pharmacology, Uropathogenic Escherichia coli drug effects
- Abstract
Coriander (Coriandruim sativum L., Apiaceae) is known for its antimicrobial activity and the aim of this study was to investigate the effect of its essential oil (CDO) against multidrug resistant uropathogenic Escherichia coli (UPEC). CDO was able to inhibit the growth of UPEC strains and propidium iodide uptake, - and electron microscopy examination suggested that bacterial structural modifications occurred. The presence of CDO reduced the MIC of gentamicin. E.coli adhesion efficiency on cell monolayers and abiotic surfaces was not affected by subMIC oil concentrations; furthermore, CDO showed cytotoxic activity towards the HEp-2 tumor cell line. These findings contribute to the knowledge about essential oils as sources of potential antimicrobial agents against uropathogenic E. coli and encourage further investigations.
- Published
- 2017
32. Boyer's Reaction and Transetherification: Mechanism and New Perspectives.
- Author
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Fraschetti C, Speranza M, Guarcini L, Roselli G, and Filippi A
- Abstract
The progress and stereochemistry of Boyer's reaction were analyzed using several simple, chiral, alcoholic substrates, a variable amount of BiBr3 and different solvents. Basic solvents inhibit the reaction, while cyclohexane works very well; thus, it was our choice for the present study. In contrast to previous works, BiBr3 behaves as a true catalyst, being not consumed during the reaction. Although poisoning of the catalyst occurs to some extent, it does not prejudice the reaction yields (>90%). Gas chromatography/mass spectrometry (GC-MS) monitoring of the reaction revealed that, for example, in the presence of alcohol , isomeric ethers transetherificate to . We propose a unifying mechanistic model for both Boyer's and transetherification reactions, in which the electronic properties of n-adducts intermediates, formed by combination of bismuth(III) of BiBr3 and oxygen atoms of alcohols and ethers, play the key role for both the reactivity and the stereochemical outcome of the reaction., (© 2016 Wiley Periodicals, Inc.)
- Published
- 2016
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33. Contact Ion Pairs on a Protonated Azamacrocycle: the Role of the Anion Basicity.
- Author
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Fraschetti C, Filippi A, Crestoni ME, Marcantoni E, Glucini M, Guarcini L, Montagna M, Guidoni L, and Speranza M
- Subjects
- Acetates chemistry, Anions chemistry, Cations chemistry, Chlorides chemistry, Fluorides chemistry, Models, Molecular, Potassium chemistry, Spectrometry, Mass, Electrospray Ionization, Aza Compounds chemistry, Macrocyclic Compounds chemistry, Protons
- Abstract
A potassium-containing hexaazamacrocyclic dication, [M•H•K](2+), is able to add in the gas phase mono- and dicarboxylate anions as well as inorganic anions by forming the corresponding monocharged adducts, the structure of which markedly depends on the basicity of the anion. With anions, such as acetate or fluoride, the neutral hexaazamacrocycle M acts as an acceptor of monosolvated K(+) ion. With less basic anions, such as trifluoroacetate or chloride, the protonated hexaazamacrocycle [M•H](+) performs the unusual functions of an acceptor of contact K(+)/anion pairs. Graphical Abstract ᅟ.
- Published
- 2016
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34. Electronic structure and conformational flexibility of D-cycloserine.
- Author
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Filippi A, Fraschetti C, Grandinetti F, Speranza M, Ponzi A, Decleva P, and Stranges S
- Subjects
- Electrons, Gases chemistry, Models, Molecular, Molecular Conformation, Photoelectron Spectroscopy, Stereoisomerism, Anti-Bacterial Agents chemistry, Cycloserine chemistry
- Abstract
The first comprehensive investigation of the effect of conformational flexibility of gaseous D-cycloserine on the valence and core electronic structures is reported here. The seven most stable conformers among the twelve structures calculated at the MP2/6-311++G** level of theory were assumed to properly describe the properties of the investigated compound. Taking into account the contribution of these isomers, the valence photoelectron spectrum (UPS) was simulated by the Outer Valence Green' s Function (OVGF) method. A different sensitivity towards the conformational flexibility of the outermost photoelectron bands was exhibited in the simulated spectrum. The comparison of the theoretical UPS with the experimental one allowed a detailed assignment of the outermost valence spectral region. The composition and bonding properties of the relevant MOs of the most stable conformers were analyzed in terms of leading Natural Bond Orbital (NBO) contributions to the HF/6-311++G** canonical MOs. The C1s, N1s, and O1s photoelectron spectra (XPS) were theoretically simulated by calculating the vertical Ionization Energies (IEs) of the relevant conformers using the ΔSCF approach. The different IE chemical shift spread of the XPS components associated with various conformers, which is expected to affect the experimental spectra, could be evaluated by simulated XPS, thus providing a new insight into the core electronic structure. The comparison of the theoretical results with the experimental ones unraveled that the atomic XPS components are not mixed by conformational flexibility of D-cycloserine, and that the specific vibronic structure of different spectral components should play a crucial role in determining different relative intensities and band shapes observed in the experiment.
- Published
- 2015
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35. Protonated Hexaazamacrocycles as Selective K(+) Receptors.
- Author
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Fraschetti C, Filippi A, Crestoni ME, Marcantoni E, Glucini M, Guarcini L, Montagna M, Guidoni L, and Speranza M
- Subjects
- Protons, Spectrometry, Mass, Electrospray Ionization, Macrocyclic Compounds chemistry, Potassium chemistry
- Abstract
Protonated hexaazamacrocycle [M•H](+) is able to detect K(+) ions present at ppb level in methanolic solutions containing 10(-5) M of Na(+) ions. The high sensitivity and selectivity of [M•H](+) for K(+) is ascribed to the favorable energy balance between the K(+) ion desolvation and its coordination to the [M•H](+) macrocycle, which allows the formation of the corresponding adduct before the Coulombic explosion of the ESI-MS nanodroplets.
- Published
- 2015
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36. Structure and conformation of protonated D-(+)-biotin in the unsolvated state.
- Author
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Fraschetti C, Filippi A, Guarcini L, Steinmetz V, and Speranza M
- Subjects
- Gases chemistry, Hydrogen Bonding, Models, Molecular, Molecular Conformation, Protons, Spectrometry, Mass, Electrospray Ionization, Biotin chemistry
- Abstract
A combined computational and infrared multiphoton dissociation (IRMPD) spectroscopic investigation shows that protonated d-(+)-biotin, formed in the gas phase by ESI-MS, acquires a folded structure with proton bonding between the ureido and valeryl carbonyls, and that only a single conformer of such a structure predominates. A uniform frequency vs distance correlation function is proposed for the O(+)-H···O and N-H···O bonds involved in the folded conformers of O2'-protonated d-(+)-biotin in the gas phase which, therefore, depends exclusively on the corresponding geometric parameters.
- Published
- 2015
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37. Role of the solvent on the stability of cycloserine under ESI-MS conditions.
- Author
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Fraschetti C, Filippi A, Mannina L, Sobolev AP, and Speranza M
- Subjects
- Acetonitriles chemistry, Cycloserine analysis, Dimerization, Drug Stability, Magnetic Resonance Spectroscopy, Methanol chemistry, Cycloserine chemistry, Solvents chemistry, Spectrometry, Mass, Electrospray Ionization methods
- Abstract
The effects of methanol (M) and acetonitrile (A) on the stability of cycloserine (1) have been studied. InfraRed Multiphoton PhotoDissociation (IRMPD) spectroscopy of the ionic species from electrospray ionization tandem mass spectrometry (ESI-MS) of 1/M and 1/A solutions points to extensive dimerization of 1 to cis-3,6-bis(aminooxymethyl)-2,5-piperidinedione (2), while the same process is not observed in the ESI-MS of 1/M solutions. 1D and 2D nuclear magnetic resonance experiments confirmed these findings by showing that partial dimerization of 1 actually takes place at room temperature in acetonitrile even before ESI-MS analysis. Comparison of nuclear magnetic resonance and IRMPD spectroscopic data from the same 1/A solution suggests that dimerization of cycloserine is enhanced in the ESI source., (Copyright © 2014 John Wiley & Sons, Ltd.)
- Published
- 2014
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38. Isomerism of Cycloserine and Its Protonated Form.
- Author
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Fraschetti C, Filippi A, Borocci S, Steinmetz V, and Speranza M
- Abstract
A comprehensive ab initio investigation has been performed on the structure and stability of the isomers of cycloserine and its protonated forms in the unsolvated state. Many conformers of cycloserine in the ketonic (K), enolic (E
4 and E2 ), and zwitterionic (Z7 and Z2 ) forms have been characterized. Enols E2 are only a few kilocalories per mole less stable than the K isomers. Enols E4 , as well as Z7 and Z2 zwitterions, are several tens of kilocalories per mole less stable than K. All the above isomeric structures exhibit pronounced isoxazolidine ring puckering, which generates very rich conformeric landscapes. The relative stability of the conformers of K, E2 , and E4 responds essentially to a complex balance between the attractive and repulsive electrostatic interactions among their functional groups. The preferred site of protonation of cycloserine in the gas phase has been also investigated computationally and experimentally by IR multiphoton dissociation (IRMPD) spectroscopy. The most basic center of cycloserine is the N(7) nitrogen atom (proton affinity (PA)=215.3 kcal mol-1 ). Another important basic site is the O(6) oxygen atom (PA=213.0 kcal mol-1 ). Their most populated conformers have been identified by IRMPD spectroscopy. Their predominance responds to the electrostatic interactions among the functional groups of the protonated molecule., (Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2014
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39. Multifunctional Macrocyclic Receptors as Templates for Aromatic Amino Acids: A Rare Example of a Highly Selective Multi-Input Multi-Output Chemo-"Logic Gate".
- Author
-
Fraschetti C, Filippi A, Crestoni ME, Ema T, and Speranza M
- Abstract
Proton-bound [M⋅H⋅G]
+ diastereomeric complexes between some chiral aromatic amino acids or dipeptides (G) and a chiral multifunctional macrocyclic receptor (M=Chirabite-A) undergo, in the gas phase, highly selective substitution and addition reactions by amines, such as 2-aminobutane and piperidine. All the [M⋅H⋅G]+ complexes follow time-dependent monoexponential decays. In some cases, the kinetic curves exhibit a plateau revealing the presence of unreactive [M⋅H⋅G]+ structures. In them, the amino acid is accommodated in the macrocycle cavity in the zwitterionic form by sharing its acidic hydrogen atoms with the pyridine nitrogen atoms of the host. The same interactions are structurally inaccessible to G=dipeptides or monofunctional amines, which then can be readily released from [M⋅H⋅G]+ . When the amino acid interacts with the amidocarbonyl oxygen atoms pointing outside the macrocycle cavity, it saves the canonical structure and can be readily displaced by the amine. The Chirabite-A may act as an efficient template for aromatic amino acids by releasing them or not depending upon the amino acid configuration and the basicity of the amine. These unique properties confer to the gas-phase diastereomeric [M⋅H⋅G]+ complexes the features of multi-input multi-output chemo-"logic gates"., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2013
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40. Unexpected behavior of diastereomeric ions in the GasPhase: a stimulus for pondering on ee measurements by ESI-MS.
- Author
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Fraschetti C, Filippi A, Crestoni ME, Ema T, and Speranza M
- Subjects
- Butanes chemistry, High-Throughput Screening Assays, Kinetics, Phenylalanine chemistry, Stereoisomerism, Gases chemistry, Ions chemistry, Spectrometry, Mass, Electrospray Ionization methods
- Abstract
The most common protocols for the quantitative determination of the enantiomeric excess (ee) of raw mixtures by ESI-MS reveal inadequate in cases where the distribution of diastereomeric derivatives diverges from the ee of original solutions. This phenomenon is attributable to a matrix effect, i.e., to the stereospecific formation of high order noncovalent adducts in the ESI droplets, which alters the actual availability of the diastereomeric species under MS analysis. In this frame, the assumption of classic protocols that the ionization correction factor q is independent on the composition of the mixture submitted to analysis is questionable. An alternative methodology is presented in this paper, which is aimed at circumventing the problem by excluding any chemical derivatization of the original raw mixture. It is based on the measurement of the actual distribution of ESI-formed proton-bound diastereomeric complexes from the enantiomeric mixture through a careful analysis of their reaction kinetics with a suitable reactant.
- Published
- 2013
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41. Enantioselective supramolecular carriers for nucleoside drugs. A thermodynamic and kinetic gas phase investigation.
- Author
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Fraschetti C, Filippi A, Crestoni ME, Villani C, Roselli G, Mortera SL, and Speranza M
- Subjects
- Drug Carriers, Gases chemistry, Kinetics, Models, Molecular, Spectrometry, Mass, Electrospray Ionization methods, Stereoisomerism, Thermodynamics, Nucleosides chemistry
- Abstract
The enantioselective interactions between chiral tetra-amidic receptors and nucleosides have been investigated by the ESI-IT-MS and ESI-FT-ICR-MS methodologies. Configurational effects on the CID fragmentation of diastereomeric [M(H)(2)•H•A](+) aggregates (A = 2'-deoxycytidine dC, citarabine (ara-C) were found to be mostly offset by isotope effect in [S(X)(2)•H•A](+) (X = H, D) differently from the results obtained on the analogues (A = cytidine C and gemcitabine G). This result points the involvement of two different nucleoside/tetraamide isoforms. The structural differences of the [M(H)(2)•H•A](+) (A = C and G) complexes vs. the [M(H)(2)•H•A](+) (dC and ara-C) ones is fully confirmed by the kinetics of their uptake of the 2-aminobutane enantiomers, measured by FT-ICR mass spectrometry. Indeed, uptake of the 2-aminobutane enantiomers by [M(H)(n)•H•A](+) (n = 1,2; A = dC and ara-C) complexes is reversible, while that by [M(H)(n)•H•A](+) (n = 1,2; A = C and G) is not. The most encouraging result concerning the measured fragmentation and kinetic differences between C and ara-C, that are just epimers, indicates the possibility to subtly modulate the non-covalent drug/receptor interactions, through the electronic properties of the 2'-substituent on the nucleoside furanose ring, and furthermore on its three-dimensional position.
- Published
- 2012
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42. Chirality effects on the IRMPD spectra of basket resorcinarene/nucleoside complexes.
- Author
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Filippi A, Fraschetti C, Piccirillo S, Rondino F, Botta B, D'Acquarica I, Calcaterra A, and Speranza M
- Subjects
- Cytarabine chemistry, Cytidine chemistry, Cytosine chemistry, Molecular Structure, Protons, Stereoisomerism, Nucleosides chemistry, Spectrophotometry, Infrared methods
- Abstract
The IRMPD spectra of the ESI-formed proton-bound complexes of the R,R,R,R- and S,S,S,S-enantiomers of a bis(diamido)-bridged basket resorcin[4]arene (R and S) with cytosine (1), cytidine (2), and cytarabine (3) were measured in the region 2800-3600 cm(-1). Comparison of the IRMPD spectra with the corresponding ONIOM (B3LYP/6-31(d):UFF)-calculated absorption frequencies allowed the assessment of the vibrational modes that are responsible for the observed spectroscopic features. All of the complexes investigated, apart from [R⋅H⋅3](+), showed similar IRMPD spectra, which points to similar structural and conformational landscapes. Their IRMPD spectra agree with the formation of several isomeric structures in the ESI source, wherein the N(3)-protonated guest establishes noncovalent interactions with the host amidocarbonyl groups that are either oriented inside the host cavity or outside it between one of the bridged side-chains and the upper aromatic nucleus. The IRMPD spectrum of the [R⋅H⋅3](+) complex was clearly different from the others. This difference is attributed to the effect of intramolecular hydrogen-bonding interactions between the C(2')-OH group and the aglycone oxygen atom of the nucleosidic guest upon repulsive interactions between the same oxygen atom and the aromatic rings of the host., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2012
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43. Cyclochiral resorcin[4]arenes as effective enantioselectors in the gas phase.
- Author
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Fraschetti C, Letzel MC, Paletta M, Mattay J, Speranza M, Filippi A, Aschi M, and Rozhenko AB
- Subjects
- Fourier Analysis, Gases chemistry, Kinetics, Macrocyclic Compounds chemistry, Models, Molecular, Phenylalanine chemistry, Stereoisomerism, Calixarenes chemistry, Phenylalanine analogs & derivatives, Spectrometry, Mass, Electrospray Ionization methods
- Abstract
The effect of cyclochirality of rccc-2,8,14,20-tetra-n-decyl-4,10,16,22-tetra-O-methylresorcin[4]arene (C) on the enantiodiscrimination of a number of chiral bidentate and tridentate aromatic and aliphatic biomolecules (G) has been investigated by nano-electrospray ionization (nano-ESI)-Fourier transform ion cyclotron resonance mass spectrometry. The experimental approach is based on the formation of diastereomeric proton-bound [C·H·G](+) complexes by nano-ESI of solutions containing an equimolar amount of quasi-enantiomers (C) together with the chiral guest (G) and the subsequent measurement of the rate of the G substitution by the attack of several achiral and chiral amines. In general, the heterochiral complexes react faster than the homochiral ones, except when G is an aminoalcoholic neurotransmitter whose complexes, beyond that, exhibit the highest enantioselectivity. The kinetic results were further supported by both collision-induced dissociation experiments on some of the relevant [C(2) ·H·G](+) three-body species and Density functional theory (DFT) calculations performed on the most selective systems., (Copyright © 2012 John Wiley & Sons, Ltd.)
- Published
- 2012
- Full Text
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44. Enantioselective supramolecular devices in the gas phase. Resorcin[4]arene as a model system.
- Author
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Fraschetti C, Letzel MC, Filippi A, Speranza M, and Mattay J
- Abstract
This review describes the state-of-art in the field of the gas-phase reactivity of diastereomeric complexes formed between a chiral artificial receptor and a biologically active molecule. The presented experimental approach is a ligand-displacement reaction carried out in a nano ESI-FT-ICR instrument, supported by a thermodynamic MS-study and molecular-mechanics and molecular-dynamics (MM/MD) computational techniques. The noncovalent ion-molecule complexes are ideal for the study of chiral recognition in the absence of complicating solvent and counterion effects.
- Published
- 2012
- Full Text
- View/download PDF
45. Unprecedented gas-phase chiroselective logic gates.
- Author
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Botta B, Fraschetti C, D'Acquarica I, Sacco F, Mattay J, Letzel MC, and Speranza M
- Subjects
- Amines chemistry, Butanes chemistry, Calixarenes chemistry, Hydrophobic and Hydrophilic Interactions, Macrocyclic Compounds chemistry, Molecular Conformation, Phenylalanine analogs & derivatives, Phenylalanine chemistry, Stereoisomerism, Gases chemistry
- Abstract
The gas-phase encounters between 2-aminobutane and proton-bound chiral resorcin[4]arene/nucleoside complexes behave in the gas phase as supramolecular "chiroselective logic gates" by releasing the nucleoside depending on the resorcin[4]arene and the 2-aminobutane configurations.
- Published
- 2011
- Full Text
- View/download PDF
46. The "bridge" game: role of the fourth player in chiral recognition.
- Author
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Fraschetti C, Pierini M, Villani C, Gasparrini F, Mortera SL, Filippi A, and Speranza M
- Subjects
- Butylamines chemistry, Gases chemistry, Mass Spectrometry, Stereoisomerism, Models, Molecular
- Abstract
A new team player: The "three-point interaction" model, which is usually employed to rationalize chiral recognition, does not account for the amazing enantioselectivity measured for the receptors of many proteic acceptors. Gas-phase experiments have indicated that at least a fourth "player" must be considered: the rigidity that a receptor opposes to distortions of its cavity resulting from noncovalent interactions with a chiral molecule (see picture)., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2011
- Full Text
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47. Does a chiral alcohol really racemize when its OH group is protected with Boyer's reaction?
- Author
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Fraschetti C, Speranza M, and Filippi A
- Abstract
Chiral reactants have been employed for assessing the real stereochemistry of the BiBr3-catalyzed synthesis of benzylic ethers, a very useful reaction for protecting alcoholic groups. The results of this investigation are in clear contrast with the conclusions of previous studies (Boyer et al., Tetrahedron 2001;57:1917-1921). Indeed, chiral GC-MS analysis of the ethereal products gives unequivocal evidence of the complete racemization of the benzylic moiety and the complete retention of configuration of the protected alcoholic substrate. Such findings make BiBr3 a powerful and stereochemically preservative catalyst for benzylation of chiral alcohols, and a potential candidate for orthogonal protecting group strategies applicable to polyhydroxy compounds., (Copyright 2009 Wiley-Liss, Inc.)
- Published
- 2010
- Full Text
- View/download PDF
48. Gas-phase enantioselectivity of chiral N-linked peptidoresorc[4]arene isomers toward dipeptides.
- Author
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Botta B, Fraschetti C, D'Acquarica I, Speranza M, Novara FR, Mattay J, and Letzel MC
- Subjects
- Amino Acid Sequence, Isomerism, Kinetics, Substrate Specificity, Dipeptides chemistry, Gases chemistry, Hydrocarbons, Aromatic chemistry, Nitrogen chemistry
- Abstract
The gas-phase enantioselectivity of cone N-linked peptidoresorc[4]arenes (generally symbolized as M) toward the homologue dipeptides (generally symbolized as A) has been evaluated by measuring the kinetics of the A release from the diastereomeric [M x H x A](+) complexes induced by (R)-(-)-2-butylamine (B). In most cases investigated, the heterochiral [M x H x A](+) complexes, namely those wherein the configuration of the A guest is opposite to that of the host M pendants, react faster (up to 5 times) than the homochiral analogues, wherein guest A guest has the same configuration of the host M pendants. The kinetic results, discussed in the light of previous MS and NMR evidence, indicate that both the efficiency and the enantioselectivity of the guest exchange reaction depend essentially on the structure and the relative stability of the diastereomeric [M x H x A](+) complexes. These, in turn, depend on the functional groups and the configuration of both the guest and the host pendants. The absence of any significant effects of the B configuration indicates that, in all systems investigated, the dipeptide guest A is predominantly located outside the host chiral cavity.
- Published
- 2009
- Full Text
- View/download PDF
49. Towards enzyme-like enantioselectivity in the gas phase: conformational control of selectivity in chiral macrocyclic dimers.
- Author
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Fraschetti C, Pierini M, Villani C, Gasparrini F, Mortera SL, and Speranza M
- Subjects
- Alanine analogs & derivatives, Alanine chemistry, Catalysis, Hydrogen Bonding, Kinetics, Models, Molecular, Molecular Structure, Spectrometry, Mass, Electrospray Ionization methods, Stereoisomerism, Thermodynamics, Gases chemistry, Macrocyclic Compounds chemistry, Molecular Conformation
- Abstract
Conformational factors in self-assembled chiral tetraamide macrocycles control their gas-phase enantioselectivity towards the ethyl ester of naphthylalanine to levels typical of enzymes.
- Published
- 2009
- Full Text
- View/download PDF
50. Gas-phase facial diastereoselectivity of equatorial and axial 4-chloro-adamant-2-yl cations.
- Author
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Fraschetti C, Novara FR, Filippi A, Speranza M, Trout NA, Adcock W, Marcantoni E, Renzi G, Roselli G, and Marcolini M
- Abstract
The acid-catalyzed addition of CH3(18)OH to 2-methylene-adamantanes bearing a chlorine atom in the 4-equatorial (1e) or 4-axial (1a) position has been investigated in the gas phase, at 760 Torr, in the 40-120 degrees C temperature range. Two different experimental approaches were employed: (1) by adding neutral CH3(18)OH to the 2-methyl-4-Cl-adamant-2-yl cation, generated by protonation of the corresponding 2-methylene-4-Cl-adamantane (the extracomplex reaction) and (2) by reaction of 2-methylene-4-Cl-adamantane with CH3(18)OH2+, generated by methylation of H2(18)O (the intracomplex reaction). The crucial role of the nature of the noncovalent intermediates involved along the reaction coordinates emerges from the difference between the results obtained in the extracomplex and intracomplex reactions for both substrates investigated. The kinetic and stereochemical results indicate that the 4-Cl substituent plays a different role depending on its equatorial or axial orientation. Examination of the experimental results in the light of MP2/6-31G* theoretical calculations provides important information about the intrinsic factors governing the facial diastereoselectivity of trigonal carbocations. The effects due to differential face solvation phenomena emerge from the comparison of the present gas-phase results with those obtained from strictly related studies in solution.
- Published
- 2009
- Full Text
- View/download PDF
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