Sequestered Fulvinol-Related Polyacetylenes in <i>Peltodoris atromaculata</i>

Ciavatta, Maria Letizia; Nuzzo, Genoveffa; Takada, Kentaro; Mathieu, Véronique; Kiss, Róbert; Villani, Guido; Gavagnin, Margherita

doi:10.1021/np500298h

Cited by 11 publications

(12 citation statements)

References 15 publications

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“…However, the hexane repeat (C-C double bond followed by four saturated CH 2 groups) is found in natural products such as the fulvinols. 38 Shorter repeat units with fewer saturated carbons are highly common in several classes of natural products including terpenes, lipids and vitamins (e.g. vitamin K).…”

Section: Discussionmentioning

confidence: 99%

Design of an efficient coherent multi-site single-molecule rectifier

Perrin

Doelman

Eelkema

et al. 2017

Phys. Chem. Chem. Phys.

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aWe propose the design of a single-molecule diode with a rectification ratio exceeding a million. The employed mechanism is based on coherent resonant charge transport across a molecule that consists of four conjugated sites coupled by non-conjugated bridges. Using density functional theory calculations, we rationalize the design of the molecule and demonstrate the crucial role of aligning the sites at a specific voltage. Rectification ratios are calculated for a series of chemical substituents and demonstrate that with careful molecular design, high rectification ratios can be achieved. Finally, we comment on the shortcomings of our approach, how further improvements can be obtained and discuss some of the experimental challenges.Molecular diodes have been attracting much attention recently, both in self-assembled monolayers 1-7 and on the single-molecule scale. [8][9][10][11][12][13][14][15][16] Even though the rectifier has been the seminal device which launched the field of single-molecule electronics, 17 up to date, their performance have many shortcomings. In particular, their rectification ratios (RR) are orders of magnitude lower than typical semiconducting rectifiers. The highest RR reported experimentally on a single-molecule junction 15 is about 600, and is no match for a semiconducting diode where ratios exceeding 10 6 are common. In that study, a molecular backbone was considered which consisted of two identical, weakly-coupled conjugated parts. In such a system, current flows coherently when both halves are on resonance, i.e., the sites are aligned with each other within the bias window. The alignment of the two sites can be modified by applying a bias voltage and/or by chemical substituents. With proper design, one can align the sites at zero bias, while misaligning them at finite bias, yielding negative differential conductance. 18 One can also align the sites at a finite bias, 15,19-22 and achieve single-molecule rectification.Based on a similar principle, here we investigate theoretically how the rectification ratio of single-molecule diodes can be significantly enhanced by the addition of more sites in series, as shown in as presented in Fig. 1b. Low RR are primarily caused by a high reverse current. Adding more sites in series leads to a strong suppression of the reverse current, thereby drastically improving the RR. However, the addition of sites comes at the cost of an increased molecular complexity and number of model parameters. In this study, we first focus on the design of a molecule which behaves as having four sites in series. For this purpose, we use density functional theory (DFT) calculations. We then investigate how the molecule can be engineered by the means of chemical substitution to align the sites at a particular bias voltage. We eventually show that the molecule designed with four sites represents a drastic improvement compared to a two-site molecule, with RR approaching 10 6 , competitive with siliconbased diodes.1 Design guidelines Fig. 1 depicts the concept of a rectifier...

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Section: Discussionmentioning

confidence: 99%

Design of an efficient coherent multi-site single-molecule rectifier

Perrin

Doelman

Eelkema

et al. 2017

Phys. Chem. Chem. Phys.

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“…165 Zalypsis®, a synthetic compound derived from jorumycin, 167 is currently in Phase II clinical trials for treatment of endometrial and cervical cancer. 168 Several studies have chemically linked the nudibranch Peltodoris atromaculata to its prey sponges Petrosia ciformis 169,170 and Haliclona fulva, 171 indicating sequestration of sponge metabolites by P. atromaculata, including sterols, 169 the polyacetylene alcohols, petroformynes 170 and fulvinol-related polyacetylenes. 170 One of these last compounds was moderately cytotoxic to the SKMEL-28 melanoma cell line.…”

Section: Chromodorididaementioning

confidence: 99%

“…170 One of these last compounds was moderately cytotoxic to the SKMEL-28 melanoma cell line. 171 The lipid and fatty acid content of the related Platydoris sp. were examined as part of a study of eight nudibranch species.…”

Section: Chromodorididaementioning

confidence: 99%

The chemistry and chemical ecology of nudibranchs

Dean

Prinsep

2017

Nat. Prod. Rep.

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Covering: up to the end of February 2017Nudibranchs have attracted the attention of natural product researchers due to the potential for discovery of bioactive metabolites, in conjunction with the interesting predator-prey chemical ecological interactions that are present. This review covers the literature published on natural products isolated from nudibranchs up to February 2017 with species arranged taxonomically. Selected examples of metabolites obtained from nudibranchs across the full range of taxa are discussed, including their origins (dietary or biosynthetic) if known and biological activity.

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“…Fulvinol ( 69b ), isolated from the sponge Reniera fulva , displays a mean GI 50 value of ∼2 μM in four cancer cell lines: murine P388 leukemia, A549 NSCLC, HT‐29 colon cancer, and SKMEL‐28 . Hydroxyl‐dehydroisofulvinol, isolated from P. atromaculata , displayed a GI 50 value of ∼3 μM against SKMEL28 melanoma cells …”

Section: Mollusk‐derived Anticancer Agentsmentioning

confidence: 99%

Marine Mollusk‐Derived Agents with Antiproliferative Activity as Promising Anticancer Agents to Overcome Chemotherapy Resistance

Ciavatta

Lefranc

Carbone

et al. 2016

Medicinal Research Reviews

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The chemical investigation of marine mollusks has led to the isolation of a wide variety of bioactive metabolites, which evolved in marine organisms as favorable adaptations to survive in different environments. Most of them are derived from food sources, but they can be also biosynthesized de novo by the mollusks themselves, or produced by symbionts. Consequently, the isolated compounds cannot be strictly considered as “chemotaxonomic markers” for the different molluscan species. However, the chemical investigation of this phylum has provided many compounds of interest as potential anticancer drugs that assume particular importance in the light of the growing literature on cancer biology and chemotherapy. The current review highlights the diversity of chemical structures, mechanisms of action, and, most importantly, the potential of mollusk‐derived metabolites as anticancer agents, including those biosynthesized by mollusks and those of dietary origin. After the discussion of dolastatins and kahalalides, compounds previously studied in clinical trials, the review covers potentially promising anticancer agents, which are grouped based on their structural type and include terpenes, steroids, peptides, polyketides and nitrogen‐containing compounds. The “promise” of a mollusk‐derived natural product as an anticancer agent is evaluated on the basis of its ability to target biological characteristics of cancer cells responsible for poor treatment outcomes. These characteristics include high antiproliferative potency against cancer cells in vitro, preferential inhibition of the proliferation of cancer cells over normal ones, mechanism of action via nonapoptotic signaling pathways, circumvention of multidrug resistance phenotype, and high activity in vivo, among others. The review also includes sections on the targeted delivery of mollusk‐derived anticancer agents and solutions to their procurement in quantity.

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Sequestered Fulvinol-Related Polyacetylenes in Peltodoris atromaculata

Cited by 11 publications

References 15 publications

Design of an efficient coherent multi-site single-molecule rectifier

Design of an efficient coherent multi-site single-molecule rectifier

The chemistry and chemical ecology of nudibranchs

Marine Mollusk‐Derived Agents with Antiproliferative Activity as Promising Anticancer Agents to Overcome Chemotherapy Resistance

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