Marine Bromotyrosine Derivatives in Spotlight: Bringing Discoveries and Biological Significance.

The Verongida order comprises several sponge families, such as Aplysinellidae, Aplysinidae, Ianthellidae, and Pseudoceratinidae, reported for producing bromotyrosine-derived compounds. First identified in 1913, bromotyrosine derivatives have since captivated interest notably for their antitumor and antimicrobial properties. To date, over 360 bromotyrosine derivatives have been reported. Our review focuses specifically on bromotyrosine derivatives newly reported from 2004 to 2023, by summarizing current knowledge about their chemical diversity and their biological activities.

New Phenylspirodrimanes from the Sponge-Associated Fungus Stachybotrys chartarum MUT 3308.

Two phenylspirodrimanes, never isolated before, stachybotrin J (1) and new stachybocin G (epi-stachybocin A) (2), along with the already reported stachybotrin I (3), stachybotrin H (4), stachybotrylactam (5), stachybotrylactam acetate (6), 2α-acetoxystachybotrylactam acetate (7), stachybotramide (8), chartarlactam B (9), and F1839-J (10) were isolated from the sponge-associated fungus Stachybotrys chartarum MUT 3308. Their structures were established based on extensive spectrometric (HRMS) and spectroscopic (1D and 2D NMR) analyses. Absolute configurations of the stereogenic centers of stachybotrin J (1), stachybocin G (2), and stachybotrin I (3), were determined by comparison of their experimental circular dichroism (CD) spectra with their time-dependent density functional theory (TD-DFT) circular dichroism (ECD) spectra. The putative structures of seventeen additional phenylspirodrimanes were proposed by analysis of their respective MS/MS spectra through a Feature-Based Molecular Networking approach. All the isolated compounds were evaluated for their cytotoxicity against five aggressive cancer cell lines (MP41, 786, 786R, CAL33, and CAL33RR), notably including two resistant human cancer cell lines (786R, CAL33RR), and compounds 5, 6, and 7 exhibited cytotoxicity with IC50 values in the range of 0.3-2.2 µM.

Marine Anticancer Agents: An Overview with a Particular Focus on Their Chemical Classes.

The marine environment is a rich source of biologically active molecules for the treatment of human diseases, especially cancer. The adaptation to unique environmental conditions led marine organisms to evolve different pathways than their terrestrial counterparts, thus producing unique chemicals with a broad diversity and complexity. So far, more than 36,000 compounds have been isolated from marine micro- and macro-organisms including but not limited to fungi, bacteria, microalgae, macroalgae, sponges, corals, mollusks and tunicates, with hundreds of new marine natural products (MNPs) being discovered every year. Marine-based pharmaceuticals have started to impact modern pharmacology and different anti-cancer drugs derived from marine compounds have been approved for clinical use, such as: cytarabine, vidarabine, nelarabine (prodrug of ara-G), fludarabine phosphate (pro-drug of ara-A), trabectedin, eribulin mesylate, brentuximab vedotin, polatuzumab vedotin, enfortumab vedotin, belantamab mafodotin, plitidepsin, and lurbinectedin. This review focuses on the bioactive molecules derived from the marine environment with anticancer activity, discussing their families, origin, structural features and therapeutic use.

Hyperbranched hydrocarbon surfactants give fluorocarbon-like low surface energies.

Two series of Aerosol-OT-analogue surfactants (sulfosuccinate-type di-BCnSS and sulfoglutarate-type di-BCnSG) with hyperbranched alkyl double tails (so-called "hedgehog" groups, carbon number n = 6, 9, 12, and 18) have been synthesized and shown to demonstrate interfacial properties comparable to those seen for related fluorocarbon (FC) systems. Critical micelle concentration (CMC), surface tension at the CMC (γCMC), and minimum area per molecule (Amin) were obtained from surface tension measurements of aqueous surfactant solutions. The results were examined for relationships between the structure of the hedgehog group and packing density at the interface. To evaluate A and B values in the Klevens equation for these hedgehog surfactants, log(CMC) was plotted as a function of the total carbon number in the surfactant double tail. A linear relationship was observed, producing B values of 0.20-0.25 for di-BCnSS and di-BCnSG, compared to a value of 0.31 for standard double-straight-tail sulfosuccinate surfactants. The lower B values of these hedgehog surfactants highlight their lower hydrophobicity compared to double-straight-tail surfactants. To clarify how hydrocarbon density in the surfactant-tail layer (ρ(layer)) affects γCMC, the ρ(layer) of each double-tail surfactant was calculated and the relationship between γCMC and ρ(layer) examined. As expected for the design of low surface energy surfactant layers, ρ(layer) was identified as an important property for controlling γCMC with higher ρ(layer), leading to a lower γCMC. Interestingly, surfactants with BC9 and BC12 tails achieved much lower γCMC, even at low ρ(layer) values of <0.55 g cm(-3). The lowest surface energy surfactant studied here was di-BC6SS, which had a γCMC of only 23.8 mN m(-1). Such a low γCMC is comparable to those obtained with short FC-tail surfactants (e.g., 22.0 mN m(-1) for the sulfosuccinate-type FC-surfactant with R = F(CF2)6CH2CH2-).

One F-octyl versus two F-butyl chains in surfactant aggregation behavior.

An easy synthetic procedure in two or three steps from perfluoroalkylethyl iodide derivatives led to six novel fluorinated carboxylates monomeric and gemini surfactants with one or two hydrophobic tails, respectively: RF(C2H4)CH(CO2(-))2,2Na(+) and [RF(C2H4)]2C(CO2(-)),Na(+), where RF = C4F9, C6F13, and C8F17. These anionic surfactants exhibited very low surface tension from 15 to 33 mN/m as well as low critical micelle concentration until 1.3 × 10(-4) mol/L. Furthermore, the surface properties of the gemini compound with two short fluoroalkyl chains (RF = C4F9) were found to be almost equal to those of the monomeric surfactant with one long fluoroalkyl chain (RF = C8F17), which could provide an interesting alternative to the bioaccumulative long-chain perfluorinated surfactant.

Giant brainlike aggregates from new fluorocarbon/hydrocarbon hybrid cationic surfactants.

A rapid synthetic procedure in two steps from perfluoroalkylethyl iodide derivatives led to 18 novel ammonium type hybrid surfactants of the general formula: R(F)(CH(2))(2)S(CH(2))(2)N(+)(CH(3))(2)R(H)Br(-) (R(F) = C(4)F(9), C(6)F(13), C(8)F(17); R(H) = C(4)H(9), C(6)H(13), C(8)H(17), C(10)H(21), C(12)H(25), C(14)H(29)). These hybrid surfactants exhibited very low surface tension (from 16 to 25 mN/m) as well as low critical micellar concentration until 1.5 × 10(-5) mol/L. A special focus was made on aggregation phenomenon as giant multilamellar "brainlike" vesicles were observed via cryogenic scanning electron microscopy (cryoSEM) and transmission electron microscopy (TEM; with a contrast agent) suggesting a high encapsulation ability and a very important specific surface of these particular organizations.

Hydrocarbon versus fluorocarbon in the electrodeposition of superhydrophobic polymer films.

To elaborate on superhydrophobic surfaces, we report the electrochemical synthesis, surface morphology, and wettability of hydrocarbon conductive polymer films obtained by the electrodeposition of polythiophene, poly(3,4-ethylenedioxythiophene) (i.e., PEDOT), and poly(3,4-ethylenedioxypyrrole) (i.e., PEDOP) derivatives. Highly hydrophobic films were obtained from n-C(14)H(29) and n-C(8)H(17) chains in the cases of polythiophenes and PEDOP, respectively. By contrast, superhydrophobic films were formed by the deposition of PEDOT substituted with n-C(10)H(21) chains (PEDOT-methyl undecanoate): static contact angle ≈ 160.6°, hysteresis ≈ 2°, and sliding angle ≈ 3°. Their surface properties were compared to those of previously reported fluorinated analogues. The water-repellent properties of PEDOT-methyl undecanoate were similar to the best surface properties obtained with fluorinated monomers. Even if the main approach for the chemical factor to build up superhydrophobic surfaces is via a coating of a fluorinated compound, this work confirms that the formation of fractal surfaces is able to achieve super-anti-wetting properties within a hydrocarbon series (less expensive with a favorable ecotoxic approach), and it opens a new path to bioinspired surfaces.

Connector ability to design superhydrophobic and oleophobic surfaces from conducting polymers.

In the aim of creating superoleophobic surfaces using monomers with short perfluorinated chains, to avoid drawbacks associated with PFOA, original semifluorinated (C(4)F(9), C(6)F(13)) 3,4-ethylenedioxypyrrole derivatives were synthesized. These monomers were obtained using the faster synthetic method than previously described with some analogues, characterized and electrochemically polymerized on gold plates. The obtained surfaces exhibited superhydrophobic (contact angle with water of 157 degrees and 158 degrees, respectively) and oleophobic properties (contact angle with hexadecane: 88 degrees and 108 degrees, respectively). The comparison between these new monomers and already published analogue EDOP6 confirms the importance of the bipolaronic form of conductive polymer for obtaining surface nanoporosity and as a consequence improving surface oleophobicity. Thus, little change in the molecule design of the connector and the spacer of the monomer can have a significant influence on the surface oleophobicity.

The design of superhydrophobic stainless steel surfaces by controlling nanostructures: A key parameter to reduce the implantation of pathogenic bacteria.

Reducing bacterial adhesion on substrates is fundamental for various industries. In this work, new superhydrophobic surfaces are created by electrodeposition of hydrophobic polymers (PEDOT-F4 or PEDOT-H8) on stainless steel with controlled topographical features, especially at a nano-scale. Results show that anti-bioadhesive and anti-biofilm properties require the control of the surface topographical features, and should be associated with a low adhesion of water onto the surface (Cassie-Baxter state) with limited crevice features at the scale of bacterial cells (nano-scale structures).

Flagella but not type IV pili are involved in the initial adhesion of Pseudomonas aeruginosa PAO1 to hydrophobic or superhydrophobic surfaces.

Over the last decades, surface biocontamination has become a major concern in food industries and medical environments where its outcomes could vary from financial losses to public health issues. Understanding adhesion mechanisms of involved microorganisms is essential to develop new strategies of prevention and control. Adhesion of Pseudomonas aeruginosa, a nosocomial pathogenic bacterium, relies on several bacterial features, among which are bacterial appendages such as flagella and type IV pili. Here, we examine the role of P. aeruginosa PAO1 flagella and type IV pili in the adhesion to abiotic surfaces with various hydrophobicities. Adhesion kinetics showed, that after 60min, flagella increased the adhesion of the strain to surfaces with high hydrophobicity while no effect was observed on hydrophilic surfaces. Flagella of adherent bacteria exhibited specific and conserved pattern on the surfaces that suggested a higher affinity of flagella for hydrophobic surfaces. Based on these results and on previous studies in the literature, we proposed a model of flagella-mediated adhesion onto hydrophobic surfaces where these appendages induce the first contact and promote the adhesion of the bacterial body. These findings suggest that anti-bioadhesive surface design should take into consideration the presence of bacterial appendages.

A spiral designed surface based on amino-perylene grafted polyacrylic acid.

This communication shows the possibility of inducing spontaneous special surface organisation by means of grafting a fluorescent aminobenzo[g,h,i]perylene derivative onto surface grown polyacrylic chains.

Superhydrophobic surfaces by electrochemical processes.

This review is an exhaustive representation of the electrochemical processes reported in the literature to produce superhydrophobic surfaces. Due to the intensive demand in the elaboration of superhydrophobic materials using low-cost, reproducible and fast methods, the use of strategies based on electrochemical processes have exponentially grown these last five years. These strategies are separated in two parts: the oxidation processes, such as oxidation of metals in solution, the anodization of metals or the electrodeposition of conducting polymers, and the reduction processed such as the electrodeposition of metals or the galvanic deposition. One of the main advantages of the electrochemical processes is the relative easiness to produce various surface morphologies and a precise control of the structures at a micro- or a nanoscale.

Recent advances in designing superhydrophobic surfaces.

The interest in superhydrophobic surfaces has grown exponentially over recent decades. Since the lotus leaf dual hierarchical structure was discovered, researchers have investigated the foundations of self-cleaning behavior. Generally, surface micro/nanostructuring combined with low surface energy of materials leads to extreme anti-wetting properties. The great number of papers on this subject attests the efforts of scientists in mimicking nature to generate superhydrophobicity. Besides the thirst for knowledge, scientists have been driven by the many possible industrial applications of superhydrophobic materials in several fields. Many methods and techniques have been developed to fabricate superhydrophobic surfaces, and the aim of this paper is to review the recent progresses in preparing manmade superhydrophobic surfaces.

Investigation of structure-surface properties relationship of semi-fluorinated polymerizable cationic surfactants.

Novel hybrid hydrocarbon/fluorocarbon ammonium type surfactant monomers (surfmers) of the general formula RF (CH2)l N(CH3)2(CH2)mOCOCH=CH2 with (RF=C4F9, C6F13, C8F17, l=4, 6, 11, and m=2-11) were synthesized and characterized. They exhibit very low surface tension as well as low critical micellar concentrations down to 1.39×10(-5)mol/L. Special attention was focused on theeffect of the polymerizable moiety, the length of the hydrocarbon spacers, and the fluorinated chains on surface activities of the reactive surfactants as compared to hydrocarbon surfmer analogs. Results indicate that the acrylic function has a pronounced effect on increasing the hydrophobic micelle character. This was confirmed by surface tensions and average surfaces occupied by these molecules at the water-gas interface. The micellar sizes were investigated by dynamic light scattering.

Stability of the hydrophilic and superhydrophobic properties of oxygen plasma-treated poly(tetrafluoroethylene) surfaces.

Poly(tetrafluoroethylene) (PTFE) materials were exposed to low and high-energy oxygen plasma, and the stability of the materials' surface was evaluated using contact angle, surface roughness, and surface chemistry characterizations. Lower-energy oxygen plasma treatments exhibited hydrophilic behavior with contact angles as low as 87°, and the higher-energy oxygen plasma treatments exhibited superhydrophobic behavior with contact angles as high as 151°. The wettability of all the treated samples as stored in air and in water was found to be stable in time as evidenced by the statistically insignificant differences in the advancing, receding, and hysteresis contact angles. Low contact angle hysteresis (θH<5°) and low sliding angle (α≈4°) were exhibited by the superhydrophobic surface. The surface morphology was found to be responsible for the changes in the wettability of the PTFE samples since (1) there was an increase in the surface rms roughness as the plasma discharge energy was increased, and (2) there were no significant changes in the observed group frequencies of the FT-IR spectra of the treated PTFE from the untreated PTFE.

Toxicity assessment of silica nanoparticles, functionalised silica nanoparticles, and HASE-grafted silica nanoparticles.

Numerous nanomaterials have recently been developed, and numerous practical applications have been found in water treatment, medicine, cosmetics, and engineering. Associative polymers, such as hydrophobically modified alkali-soluble emulsion (HASE) systems are involved in several applications and have been extensively studied due to their ability to form three-dimensional networked gels. However, the data on the potential environmental effects of this polymers are scarce. The aim of this study is to assess the effect of functionalisation of silica nanoparticles, and coupling of functionalised silica nanoparticles to the associative polymer HASE on their toxicity. Thus, acute and chronic toxicity tests included a modified acute test (72 h) using daphnies, algae, and plants as model organisms. Gradient of toxicity varied with the tested organisms. Our results revealed that the functionalised nanoparticules and NP grafted polymer cause a global decrease in toxicity compared to commercial nanoparticule and HASE polymer.

Covalent layer-by-layer assembled superhydrophobic organic-inorganic hybrid films.

Using the concept of covalent layer-by-layer assembly (covalent LbL), used until now for the elaboration of films from polymers or dendrimers, we have constructed hybrid organic/inorganic surfaces by alternating different layers of amino-functionalized silica nanoparticles (295 nm diameter) and epoxy-functionalized smaller silica nanoparticles (20 nm diameter). The so-realized macromolecular edifice leads to a hierarchical integration of nanoscale textures. Then hydrophobization of the last layer of amino-functionalized silica particles was carried out by grafting a new designed highly fluorinated aldehyde, creating a monomolecular layer via the formation of an imine function. Five highly fluorinated surfaces were built, and their water-repellent abilities were directly correlated to the surface topologies (i.e., the number of layers of silica nanoparticles and their organization on the glass support). The hydrophobicity increased with the number of layers and stable highly water-repellent surfaces (static contact angle with water of 150+/-3 degrees and a contact angle hysteresis of 12 degrees) were obtained with the alternation of nine layers. This result demonstrates the possibility to construct covalent LbL edifices with functionalized silica nanoparticles of different sizes and open this field for the elaboration of responsive, sensing, and therapeutic surfaces with improved film stability.

Polymerizable semi-fluorinated gemini surfactants designed for antimicrobial materials.

Introduction of biocide monomers during the process of polymerization is one of promising approaches in the development of new permanent non leaching biocide materials. In this perspective, new polymerizable semi-fluorinated gemini surfactants, with quaternary ammonium groups as polar heads and an acrylic function as the polymerizable moiety, were synthesized and tested to evaluate their surface active properties alongside with their antibacterial and antifungal properties. Four microbial strains, known for their implication in nosocomial infections, were used to perform the study: Pseudomonas aeruginosa, Staphylococcus aureus, Candida albicans and Aspergillus niger. The biocide efficacy measured by bacterial and fungal growth inhibition expressed as MIC (minimal inhibitory concentration) and MLC (minimal lethal concentration) values was discussed as a function of molecular parameters. As compared to homologue compounds without acrylic part, this study shows that even the introduction of a polymerizable moiety allows to keep remarkable both surfactant and bacteriostatic activities, and allows us to envisage the use of these surfactant monomers to build up advanced biocide materials. Moreover, semi-fluorinated gemini surfactant monomers with an amide connector came out as broad spectrum biocides (against Gram positive and negative bacteria and fungi).

Preparation and antimicrobial behaviour of quaternary ammonium thiol derivatives able to be grafted on metal surfaces.

New thiol derivatives containing a quaternary ammonium group bearing variable hydrocarbon chains via an amide connector or not between the sulphur and nitrogen atoms were synthesised with the future aim to be grafted on metal surfaces for obtaining contact-active auto-bactericidal surfaces. Their biostatic and bactericidal activities were evaluated against four microbial strains (Pseudomonas aeruginosa, Staphylococcus aureus, Aspergillus niger and Candida albicans). The presence of the thiol and amide functions in these surfactants was discussed in relation with the antimicrobial activity along with the influence of the length of alkyl chains in order to determine which molecular parameters are 'critical' for biological activity, and consequently what molecules must be chosen for grafting on metal surface.