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"Caputi, Lorenzo"
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Biosynthesis of strychnine
2022
Strychnine is a natural product that, through isolation, structural elucidation and synthetic efforts, shaped the field of organic chemistry. Currently, strychnine is used as a pesticide to control rodents
1
because of its potent neurotoxicity
2
,
3
. The polycyclic architecture of strychnine has inspired chemists to develop new synthetic transformations and strategies to access this molecular scaffold
4
, yet it is still unknown how plants create this complex structure. Here we report the biosynthetic pathway of strychnine, along with the related molecules brucine and diaboline. Moreover, we successfully recapitulate strychnine, brucine and diaboline biosynthesis in
Nicotiana benthamiana
from an upstream intermediate, thus demonstrating that this complex, pharmacologically active class of compounds can now be harnessed through metabolic engineering approaches.
The biosynthetic pathway of strychnine, brucine and diaboline is described, and the biosynthesis of these complex, pharmacologically active compounds has been successfully recapitulated in
Nicotiana benthamiana
from an upstream intermediate.
Journal Article
Single-cell multi-omics in the medicinal plant Catharanthus roseus
by
Serna Guerrero, Delia Ayled
,
Gase, Klaus
,
Vaillancourt, Brieanne
in
631/1647
,
631/449
,
631/45
2023
Advances in omics technologies now permit the generation of highly contiguous genome assemblies, detection of transcripts and metabolites at the level of single cells and high-resolution determination of gene regulatory features. Here, using a complementary, multi-omics approach, we interrogated the monoterpene indole alkaloid (MIA) biosynthetic pathway in
Catharanthus roseus
, a source of leading anticancer drugs. We identified clusters of genes involved in MIA biosynthesis on the eight
C. roseus
chromosomes and extensive gene duplication of MIA pathway genes. Clustering was not limited to the linear genome, and through chromatin interaction data, MIA pathway genes were present within the same topologically associated domain, permitting the identification of a secologanin transporter. Single-cell RNA-sequencing revealed sequential cell-type-specific partitioning of the leaf MIA biosynthetic pathway that, when coupled with a single-cell metabolomics approach, permitted the identification of a reductase that yields the bis-indole alkaloid anhydrovinblastine. We also revealed cell-type-specific expression in the root MIA pathway.
The medicinal plant
Catharanthus roseus
is a source of leading anticancer drugs. The monoterpene indole alkaloid (MIA) biosynthetic pathway in
C. roseus
has now been analyzed using a complementary, multi-omics, single-cell approach. This identified clusters of genes involved in MIA biosynthesis and cell-type-specific partitioning in the MIA biosynthetic pathway.
Journal Article
The Advent of Indium Selenide: Synthesis, Electronic Properties, Ambient Stability and Applications
by
Cupolillo, Anna
,
Gürbulak, Bekir
,
Duman, Songül
in
angle-resolved photoemission spectroscopy
,
Bridgman-Stockbarger growth
,
Broadband
2017
Among the various two-dimensional semiconductors, indium selenide has recently triggered the interest of scientific community, due to its band gap matching the visible region of the electromagnetic spectrum, with subsequent potential applications in optoelectronics and especially in photodetection. In this feature article, we discuss the main issues in the synthesis, the ambient stability and the application capabilities of this novel class of two-dimensional semiconductors, by evidencing open challenges and pitfalls. In particular, we evidence how the growth of single crystals with reduced amount of Se vacancies is crucial in the road map for the exploitation of indium selenide in technology through ambient-stable nanodevices with outstanding values of both mobility of charge carriers and ON/OFF ratio. The surface chemical reactivity of the InSe surface, as well as applications in the fields of broadband photodetection, flexible electronics and solar energy conversion are also discussed.
Journal Article
Removal of mercury(II) from aqueous solution by partially reduced graphene oxide
by
Arias Arias, Fabian
,
Nuñez, Adriana
,
Pisarra, Michele
in
704/172/169
,
704/172/4081
,
Adsorption
2022
Mercury (Hg(II)) has been classified as a pollutant and its removal from aqueous sources is considered a priority for public health as well as ecosystem protection policies. Oxidized graphenes have attracted vast interest in water purification and wastewater treatment. In this report, a partially reduced graphene oxide is proposed as a pristine adsorbent material for Hg(II) removal. The proposed material exhibits a high saturation Hg(II) uptake capacity of 110.21 mg g
−1
, and can effectively reduce the Hg(II) concentration from 150 mg L
−1
to concentrations smaller than 40 mg L
−1
, with an efficiency of about 75% within 20 min. The adsorption of Hg(II) on reduced graphene oxide shows a mixed physisorption–chemisorption process. Density functional theory calculations confirm that Hg atom adsorbs preferentially on clean zones rather than locations containing oxygen functional groups. The present work, therefore, presents new findings for Hg(II) adsorbent materials based on partially reduced graphene oxide, providing a new perspective for removing Hg(II).
Journal Article
The Adsorption of Methylene Blue on Eco-Friendly Reduced Graphene Oxide
by
Arias Arias, Fabian
,
Arias, Melvin
,
Vacacela Gomez, Cristian
in
Adsorption
,
Cationic dyes
,
Chemisorption
2020
Recently, green-prepared oxidized graphenes have attracted huge interest in water purification and wastewater treatment. Herein, reduced graphene oxide (rGO) was prepared by a scalable and eco-friendly method, and its potential use for the removal of methylene blue (MB) from water systems, was explored. The present work includes the green protocol to produce rGO and respective spectroscopical and morphological characterizations, as well as several kinetics, isotherms, and thermodynamic analyses to successfully demonstrate the adsorption of MB. The pseudo-second-order model was appropriated to describe the adsorption kinetics of MB onto rGO, suggesting an equilibrium time of 30 min. Otherwise, the Langmuir model was more suitable to describe the adsorption isotherms, indicating a maximum adsorption capacity of 121.95 mg g−1 at 298 K. In addition, kinetics and thermodynamic analyses demonstrated that the adsorption of MB onto rGO can be treated as a mixed physisorption–chemisorption process described by H-bonding, electrostatic, and π − π interactions. These results show the potential of green-prepared rGO to remove cationic dyes from wastewater systems.
Journal Article
Toward Large-Scale Production of Oxidized Graphene
by
Veltri, Francesco
,
Arias, Melvin
,
Vacacela Gomez, Cristian
in
citric acid
,
Communication
,
graphene
2020
The oxidative exfoliation of graphite is a promising approach to the large-scale production of graphene. Conventional oxidation of graphite essentially facilitates the exfoliation process; however, the oxidation procedure releases toxic gases and requires extensive, time-consuming steps of washing and reduction to convert exfoliated graphene oxide (GO) into reduced graphene oxide (rGO). Although toxic gases can be controlled by modifying chemical reactions, filtration, dialysis, and extensive sonication are unfavorable for large-scale production. Here, we report a complete, scalable, and green synthesis of GO, without NaNO3, followed by reduction with citric acid (CA). This approach eliminates the generation of toxic gases, simplifies the washing steps, and reduces the time required to prepare rGO. To validate the proposed method, we present spectroscopical and morphological studies, using energy-dispersive X-ray spectroscopy (EDS), UV-visible spectroscopy, infrared spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Thermal gravimetric analysis (TGA) is used to analyze the thermal properties of GO and rGO. This eco-friendly method proposes a complete guideline protocol toward large-scale production of oxidized graphene, with potential applications in supercapacitors, fuel cells, composites, batteries, and biosensors.
Journal Article
Differences of skin carotenoids and adherence to the Mediterranean Diet pattern in adults from Southern Italy and Dominican Republic
by
Bonofiglio, Daniela
,
Villegas Figueroa, Melisa
,
Cesario, Mirko
in
"Planeterranean" Diet: Globally Extending the Health Benefits of the Mediterranean Diet
,
Adult
,
Adults
2024
Background
The measurement of the skin carotenoids using the Veggie Meter® has emerged as a rapid objective method for assessing fruit and vegetable intake, highly recommended by the Mediterranean Diet (MD), which represents one of the healthiest dietary patterns, worldwide. This study aimed to examine differences in skin carotenoid content and degree of adherence to the MD pattern between two adult populations from Southern Italy and the Dominican Republic.
Methods
This cross-sectional study enrolled a total of 995 adults, 601 subjects from Italy and 394 from the Dominican Republic. All participants underwent anthropometric measurements and skin carotenoid assessment by Veggie Meter®. Adherence to the MD and lifestyle were evaluated using the Mediterranean Diet Adherence Screener (MEDAS) and the Mediterranean Lifestyle Index (MEDLIFE) questionnaires. Correlations between the skin carotenoid and MEDAS score were estimated using Pearson’s correlation coefficient. Multiple linear regression models were created to determine variables that affect skin carotenoid score for both populations.
Results
Mean total skin carotenoids were higher in the Italian compared to the Dominican Republic population (342.4 ± 92.4
vs
282.9 ± 90.3; p < 0.005) regardless of sex (women: 318.5 ± 88.9
vs
277.3 ± 91.9, p < 0.005 and men: 371.7 ± 88.3
vs
289.5 ± 88.1, p < 0.005), and remaining statistically significant after age-adjustment of the Dominican Republic sample. Using the MEDAS questionnaire, we found a higher MD adherence score in the Italian than in the Dominican Republic population also after age-adjusting data (7.8 ± 2.1
vs
6.2 ± 3.7; p < 0.005) and even when categorized by sex (Italian
vs
age-adjusted Dominican Republic women: 7.9 ± 2.1
vs
6.3 ± 2.6; Italian vs age-adjusted Dominican Republic men: 7.7 ± 2.2
vs
6.0 ± 4.7; p < 0.005). Using the MEDLIFE test, total Italians presented a lower score with respect to the age-adjusted Dominican Republic population (3.2 ± 1.2
vs
3.4 ± 1.4; p < 0.05). In multiple regression analysis, skin carotenoids were associated with sex and negatively associated with BMI in the Italian population (sex: β: 54.95; 95% CI: 40.11, 69.78; p < 0.0001; BMI: β: − 1.60; 95% CI: − 2.98,0.86; p = 0.03), while they resulted associated with age and sex in the Dominican Republic population (age: β: 2.76; 95% CI: 1.92, 3.56; p < 0.001; sex: β: 23.29; 95% CI: 5.93, 40.64; p = 0.009). Interestingly, skin carotenoids were positively correlated with MEDAS score in both populations (Italy: r = 0.03, p < 0.0001, Dominican Republic: r = 0.16, p = 0.002).
Conclusions
This study provides the assessment of the adherence to the MD and skin carotenoid content in adults living in Southern Italy and the Dominican Republic, showing a higher MD adherence score and a skin carotenoid content in inhabitants from the Mediterranean region. Our findings highlight the need to globally encourage fruit and vegetable intake, particularly in non-Mediterranean area.
Journal Article
Gibberellin metabolism in Vitis vinifera L. during bloom and fruit-set: functional characterization and evolution of grapevine gibberellin oxidases
by
Moretto, Marco
,
Vrhovsek, Urska
,
Giacomelli, Lisa
in
Arabidopsis thaliana
,
Berries
,
bioactive properties
2013
Gibberellins (GAs) are involved in the regulation of flowering and fruit-set in grapes (Vitis vinifera L.), but the molecular mechanisms behind this process are mostly unknown. In this work, the family of grapevine GA oxidases involved in the biosynthesis and deactivation of GAs was characterized. Six putative GA 20-oxidase (GA20ox), three GA 3-oxidase (GA3ox), and eight GA 2-oxidase (GA2ox) proteins, the latter further divided into five C19-GA 2ox and three C20-GA2ox proteins, were identified. Phylogenetic analyses suggest a common origin of the GA3ox and C19-GA2ox groups and challenge previous evolutionary models. In vitro analysis revealed that all GA3ox and GA20ox enzymes prefer substrates of the non-13-hydroxylation pathway. In addition, ectopic expression of GA2ox genes in Arabidopsis thaliana confirmed the activity of their encoded proteins in vivo. The results show that bioactive GA1 accumulates in opening grapevine flowers, whereas at later developmental stages only GA4 is detected in the setting fruit. By studying the expression pattern of the grapevine GA oxidase genes in different organs, and at different stages of flowering and fruit-set, it is proposed that the pool of bioactive GAs is controlled by a fine regulation of the abundance and localization of GA oxidase transcripts.
Journal Article
Structural investigation of heteroyohimbine alkaloid synthesis reveals active site elements that control stereoselectivity
by
Stavrinides, Anna
,
Tatsis, Evangelos C.
,
Foureau, Emilien
in
14/63
,
631/449/1659
,
631/449/2667
2016
Plants produce an enormous array of biologically active metabolites, often with stereochemical variations on the same molecular scaffold. These changes in stereochemistry dramatically impact biological activity. Notably, the stereoisomers of the heteroyohimbine alkaloids show diverse pharmacological activities. We reported a medium chain dehydrogenase/reductase (MDR) from
Catharanthus roseus
that catalyses formation of a heteroyohimbine isomer. Here we report the discovery of additional heteroyohimbine synthases (HYSs), one of which produces a mixture of diastereomers. The crystal structures for three HYSs have been solved, providing insight into the mechanism of reactivity and stereoselectivity, with mutation of one loop transforming product specificity. Localization and gene silencing experiments provide a basis for understanding the function of these enzymes
in vivo
. This work sets the stage to explore how MDRs evolved to generate structural and biological diversity in specialized plant metabolism and opens the possibility for metabolic engineering of new compounds based on this scaffold.
The stereochemistry of the plant heteroyohimbine alkaloids is a key factor determining their diverse biological activities. Here, the authors carry out structural, localization and genetic experiments to understand the mechanism of stereoselectivity for three heteroyohimbine synthases and to identify their function
in vivo
.
Journal Article
Role of Graphene Oxide and Reduced Graphene Oxide in Electric Double-Layer Capacitors: A Systematic Review
by
Guapi, Alberto
,
Romero, Paul
,
Straface, Salvatore
in
Business metrics
,
Capacitance
,
Capacitors
2024
The evolution of electric double-layer capacitors (EDLCs) has significantly benefited from advancements in graphene-based materials, particularly graphene oxide (GO) and reduced graphene oxide (rGO). This systematic review consolidates and analyzes existing research on the roles of GO and rGO in enhancing the performance of EDLCs, focusing on synthesis methods, electrode fabrication, electrolytes, and performance metrics such as capacitance, energy density, and cycling stability. Following the PICOS and PRISMA frameworks, a comprehensive literature search was conducted across Scopus, Web of Science, PubMed, and IEEE Xplore, covering the period from 2010 to 2023. A total of 128 articles were initially identified, with 27 studies meeting the inclusion criteria after rigorous screening and full-text analysis. Key findings reveal that the incorporation of GO and rGO in EDLCs leads to significant improvements in specific capacitance, energy density, and cycling stability. Notable advancements include novel synthesis techniques and composite materials such as nitrogen-doped graphene, graphene/polyaniline hybrids, and various metal oxide–graphene composites, which exhibit superior electrochemical performance. However, challenges such as material scalability, environmental sustainability, and consistency in synthesis methods remain. This review stresses the great potential of GO and rGO in the development of high-performance EDLCs and highlights the need for continued research to address existing challenges and further optimize material properties and fabrication techniques.
Journal Article