Pegylated Phosphine Ligands in Iridium(I) Catalyzed Hydrogen Isotope Exchange Reactions in Aqueous Buffers.

The synthesis of a water-soluble, phosphine-pegylated iridium(I) catalyst and its application in hydrogen isotope exchange (HIE) reactions in buffer is reported. The longer polyethylene glycol side chains on the phosphine increased the water solubility independently from the pH. HIE reactions of polar substrates in protic solvents were studied. DFT calculations gave further insides into the catalytic processes. The scope and limitation of the pegylated catalyst was studied in HIE reactions of several complex compounds in borax buffer at pH 9 and the best conditions were applied in a tritium experiment with the drug telmisartan.

Hemophagocytic syndrome related by EBV infection: case report.

A 34-year-old woman of Asian origin with diffuse lymphadenopathy and hepatosplenomegaly in hemophagocytic syndrome induced by Epstein Barr Virus (EBV) infection. The rapidity of progression of clinical manifestations lead to early orotracheal intubation and death due to multiple organ failure (MOF).

Effects of Structurally Different Tertiary Amines on the Properties of Quaternized Anionic Exchange Membranes Potentially Applicable for Water Electrolysis.

In this work, two structurally different monoamines (trimethylamine [TMA] and N-methylpiperidine [N-MPip]) are used for the amination of a g-VBC-15 graft copolymer, obtained by the functionalization of a mechanically robust, commercially available styrene-butadiene block copolymer (SB) with vinylbenzyl chloride (VBC) via solution free-radical polymerization. Results demonstrate that g-VBC-15-based membranes quaternized with TMA have superior electrochemical performance than N-MPip counterparts; while, the mechanical properties are good and only slightly inferior to those of N-MPip. Therefore, TMA is the selected monoamine to be alternatively mixed with two polyamines (tetramethyl-1,3-propanediamine [TMPDA] and N,N,N',N'',N''-pentamethyldiethylenetriamine [PMDETA]) into different proportions, in order to modulate the average functionality of the amination mixture in terms of number of amine functional groups available for the quaternization reaction of the membranes. g-VBC-15-based membranes derived therefrom are extensively characterized to assess their thermal, mechanical, and ex situ electrochemical properties. Results indicate that membranes quaternized with a TMA/PMDETA mixture (90:10 in mole) display the highest conductivity among all the investigated membranes aminated with polyamine-based mixtures. Moreover, they have comparable mechanical and electrochemical properties to those quaternized with TMA, while exhibiting a reduced water uptake.

Impact of Temperature on the Chiroptical Properties of Thin Films of Chiral Thiophene-based Oligomers.

According to the theoretical model based on the Mueller matrix approach, the experimental electronic circular dichroism (ECD) for thin films of chiral organic dyes can be expressed as the sum of several contributions, two of which are the most significant: 1) an intrinsic component (CDiso) invariant upon sample orientation, reflecting the molecular and/or supramolecular chirality, due to 3D-chiral nanoscopic structures; 2) a non-reciprocal component (LDLB) which inverts its sign upon sample flipping, which arises from the interaction of linear dichroism and linear birefringence in locally anisotropic domains, expression of 2D-chiral micro/mesoscopic structures. In this work, we followed in parallel through ECD and differential scanning calorimetry (DSC) the temperature evolution of the supramolecular arrangements of thin films of five structurally related chiral thiophene-based oligomers with different LDLB/CDiso ratio. By increasing the temperature, regardless of phase transitions observed by DSC analysis, systems with strong CDiso revealed no changes in the ECD spectrum, while compounds with dominant LDLB contribution underwent a gradual (and reversible) reduction of (apparent) ECD signals. These findings demonstrated that the concomitant occurrence of intrinsic and non-reciprocal components in the ECD spectrum of thin films of chiral organic dyes is strictly correlated with solid-state organizations of different stability.

Preparation and Characterization of Zinc(II)-Based Lewis/Brønsted Acidic Deep Eutectic Solvents.

Lewis/Brønsted acidic deep eutectic solvents (LBDESs) are a recent class of solvents that combine the two types of acidity. In some cases, this synergy leads to enhanced catalytic properties for many reactions and applications. For this reason, it is important to discover more LBDESs. In this work, we prepared and characterized four different zinc(II)-based LBDESs, mixing ZnCl2 and various Brønsted acids: acetic, glycolic, levulinic, and formic acids. Apart from the latter, for which the corresponding DES is not thermally stable, the samples have been characterized in terms of density, viscosity, and conductivity. Notably, as zinc(II) is a diamagnetic metal, all of them are suitable for NMR spectroscopy, for example, for kinetic and mechanistic studies.

An Electron Spin Resonance Study Comparing Nanometer-Nanosecond Dynamics in Diblock Copolymers and Their Poly(methyl Methacrylate) Binary Blends.

Block copolymers are a class of materials that are particularly interesting with respect to their capability to self-assemble in ordered structures. In this context, the coupling between environment and dynamics is particularly relevant given that movements at the molecular level influence various properties of macromolecules. Mixing the polymer with a second macromolecule appears to be an easy method for studying these relationships. In this work, we studied blends of poly(methyl methacrylate) (PMMA) and a block copolymer composed of PMMA as the first block and poly(3-methyl-4-[6-(methylacryloyloxy)-hexyloxy]-4'-pentyloxy azobenzene) as the second block. The relaxational properties of these blends were investigated via electron spin resonance (ESR) spectroscopy, which is sensitive to nanometric length scales. The results of the investigations on the blends were related to the dynamic behavior of the copolymers. At the nanoscale, the study revealed the presence of heterogeneities, with slow and fast dynamics available for molecular reorientation, which are further modulated by the ability of the block copolymers to form supramolecular structures. For blends, the heterogeneities at the nanoscale were still detected. However, it was observed that the presence of the PMMA as a major component of the blends modified their dynamic behavior.

Amphiphilic Fluorinated Unimer Micelles as Nanocarriers of Fluorescent Probes for Bioimaging.

The unique self-assembly properties of unimer micelles are exploited for the preparation of fluorescent nanocarriers embedding hydrophobic fluorophores. Unimer micelles are constituted by a (meth)acrylate copolymer with oligoethyleneglycol and perflurohexylethyl side chains (PEGMA90-co-FA10) in which the hydrophilic and hydrophobic comonomers are statistically distributed along the polymeric backbone. Thanks to hydrophobic interactions in water, the amphiphilic copolymer forms small nanoparticles (<10 nm), with tunable properties and functionality. An easy procedure for the encapsulation of a small hydrophobic molecule (C153 fluorophore) within unimer micelles is presented. UV-vis, fluorescence, and fluorescence anisotropy spectroscopic experimental data demonstrate that the fluorophore is effectively embedded in the nanocarriers. Moreover, the nanocarrier positively contributes to preserve the good emissive properties of the fluorophore in water. The efficacy of the dye-loaded nanocarrier as a fluorescent probe is tested in two-photon imaging of thick ex vivo porcine scleral tissue.

The Nanostructured Self-Assembly and Thermoresponsiveness in Water of Amphiphilic Copolymers Carrying Oligoethylene Glycol and Polysiloxane Side Chains.

Amphiphilic copolymer self-assembly is a straightforward approach to obtain responsive micelles, nanoparticles, and vesicles that are particularly attractive for biomedicine, i.e., for the delivery of functional molecules. Here, amphiphilic copolymers of hydrophobic polysiloxane methacrylate and hydrophilic oligo (ethylene glycol) methyl ether methacrylate with different lengths of oxyethylenic side chains were synthesized via controlled RAFT radical polymerization and characterized both thermally and in solution. In particular, the thermoresponsive and self-assembling behavior of the water-soluble copolymers in water was investigated via complementary techniques such as light transmittance, dynamic light scattering (DLS), and small-angle X-ray scattering (SAXS) measurements. All the copolymers synthesized were thermoresponsive, displaying a cloud point temperature (Tcp) strongly dependent on macromolecular parameters such as the length of the oligo(ethylene glycol) side chains and the content of the SiMA counits, as well as the concentration of the copolymer in water, which is consistent with a lower critical solution temperature (LCST)-type behavior. SAXS analysis revealed that the copolymers formed nanostructures in water below Tcp, whose dimension and shape depended on the content of the hydrophobic components in the copolymer. The hydrodynamic diameter (Dh) determined by DLS increased with the amount of SiMA and the associated morphology at higher SiMA contents was found to be pearl-necklace-micelle-like, composed of connected hydrophobic cores. These novel amphiphilic copolymers were able to modulate thermoresponsiveness in water in a wide range of temperatures, including the physiological temperature, as well as the dimension and shape of their nanostructured assemblies, simply by varying their chemical composition and the length of the hydrophilic side chains.

Vinylbenzyl Chloride/Styrene-Grafted SBS Copolymers via TEMPO-Mediated Polymerization for the Fabrication of Anion Exchange Membranes for Water Electrolysis.

In this work, a commercial SBS was functionalized with the 2,2,6,6-tetramethylpiperidin-N-oxyl stable radical (TEMPO) via free-radical activation initiated with benzoyl peroxide (BPO). The obtained macroinitiator was used to graft both vinylbenzyl chloride (VBC) and styrene/VBC random copolymer chains from SBS to create g-VBC-x and g-VBC-x-co-Sty-z graft copolymers, respectively. The controlled nature of the polymerization as well as the use of a solvent allowed us to reduce the extent of the formation of the unwanted, non-grafted (co)polymer, thereby facilitating the graft copolymer's purification. The obtained graft copolymers were used to prepare films via solution casting using chloroform. The -CH2Cl functional groups of the VBC grafts were then quantitatively converted to -CH2(CH3)3N+ quaternary ammonium groups via reaction with trimethylamine directly on the films, and the films, therefore, were investigated as anion exchange membranes (AEMs) for potential application in a water electrolyzer (WE). The membranes were extensively characterized to assess their thermal, mechanical, and ex situ electrochemical properties. They generally presented ionic conductivity comparable to or higher than that of a commercial benchmark as well as higher water uptake and hydrogen permeability. Interestingly, the styrene/VBC-grafted copolymer was found to be more mechanically resistant than the corresponding graft copolymer not containing the styrene component. For this reason, the copolymer g-VBC-5-co-Sty-16-Q with the best balance of mechanical, water uptake, and electrochemical properties was selected for a single-cell test in an AEM-WE.

Nitroxide-Containing Amphiphilic Random Terpolymers for Marine Antifouling and Fouling-Release Coatings.

Two types of amphiphilic random terpolymers, poly(ethylene glycol methyl ether methacrylate)-ran-poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate)-ran-poly(polydimethyl siloxane methacrylate) (PEGMEMA-r-PTMA-r-PDMSMA), were synthesized and evaluated for antifouling (AF) and fouling-release (FR) properties using diverse marine fouling organisms. In the first stage of production, the two respective precursor amine terpolymers containing (2,2,6,6-tetramethyl-4-piperidyl methacrylate) units (PEGMEMA-r-PTMPM-r-PDMSMA) were synthesized by atom transfer radical polymerization using various comonomer ratios and two initiators: alkyl halide and fluoroalkyl halide. In the second stage, these were selectively oxidized to introduce nitroxide radical functionalities. Finally, the terpolymers were incorporated into a PDMS host matrix to create coatings. AF and FR properties were examined using the alga Ulva linza, the barnacle Balanus improvisus, and the tubeworm Ficopomatus enigmaticus. The effects of comonomer ratios on surface properties and fouling assay results for each set of coatings are discussed in detail. There were marked differences in the effectiveness of these systems against the different fouling organisms. The terpolymers had distinct advantages over monopolymeric systems across the different organisms, and the nonfluorinated PEG and nitroxide combination was identified as the most effective formulation against B. improvisus and F. enigmaticus.

Posidonia oceanica (L.) (Delile, 1813) extracts as a potential booster biocide in fouling-release coatings.

Since the banning of tributyltin, the addition of inorganic (metal oxides) and organic (pesticides, herbicides) biocides in antifouling paint has represented an unavoidable step to counteract biofouling and the resulting biodeterioration of submerged surfaces. Therefore, the development of new methods that balance antifouling efficacy with environmental impact has become a topic of great importance. Among several proposed strategies, natural extracts may represent one of the most suitable alternatives to the widely used toxic biocides. Posidonia oceanica is one of the most representative organisms of the Mediterranean Sea and contains hundreds of bioactive compounds. In this study, we prepared, characterized, and assessed a hydroalcoholic extract of P. oceanica and then compared it to three model species. Together, these four species belong to relevant groups of biofoulers: bacteria (Aliivibrio fischeri), diatoms (Phaeodactylum tricornutum), and serpulid polychaetes (Ficopomatus enigmaticus). We also added the same P. oceanica extract to a PDMS-based coating formula. We tested this coating agent with Navicula salinicola and Ficopomatus enigmaticus to evaluate both its biocidal performance and its antifouling properties. Our results indicate that our P. oceanica extract provides suitable levels of protection against all the tested organisms and significantly reduces adhesion of N. salinicola cells and facilitates their release in low-intensity waterflows.

Polyethylene Glycol-b-poly(trialkylsilyl methacrylate-co-methyl methacrylate) Hydrolyzable Block Copolymers for Eco-Friendly Self-Polishing Marine Coatings.

Hydrolyzable block copolymers consisting of a polyethylene glycol (PEG) first block and a random poly(trialkylsilyl methacrylate (TRSiMA, R = butyl, isopropyl)-co-methyl methacrylate (MMA)) second block were synthesized by RAFT polymerization. Two PEGs with different molar masses (Mn = 750 g/mol (PEG1) and 2200 g/mol (PEG2)) were used as macro-chain transfer agents and the polymerization conditions were set in order to obtain copolymers with a comparable mole content of trialkylsilyl methacrylate (~30 mole%) and two different PEG mole percentages of 10 and 30 mole%. The hydrolysis rates of PEG-b-(TRSiMA-co-MMA) in a THF/basic (pH = 10) water solution were shown to drastically depend on the nature of the trialkylsilyl groups and the mole content of the PEG block. Films of selected copolymers were also found to undergo hydrolysis in artificial seawater (ASW), with tunable erosion kinetics that were modulated by varying the copolymer design. Measurements of the advancing and receding contact angles of water as a function of the immersion time in the ASW confirmed the ability of the copolymer film surfaces to respond to the water environment as a result of two different mechanisms: (i) the hydrolysis of the silylester groups that prevailed in TBSiMA-based copolymers; and (ii) a major surface exposure of hydrophilic PEG chains that was predominant for TPSiMA-based copolymers. AFM analysis revealed that the surface nano-roughness increased upon immersion in ASW. The erosion of copolymer film surfaces resulted in a self-polishing, antifouling behavior against the diatom Navicula salinicola. The amount of settled diatoms depended on the hydrolysis rate of the copolymers.

Use of a human wrist blood pressure monitor for arterial blood pressure measurements in normotensive conscious dogs in comparison to veterinary high-definition oscillometry.

BACKGROUND: The gold standard in canine blood pressure (BP) measurement is the invasive method; however, non-invasive blood pressure measurement techniques (NIBP) are more commonly used. The lack of small, lightweight, cheap, fast and portable NIBP still remains a point to improve in the emergency setting. KEY FINDINGS: A human wrist blood pressure (WBP) device was evaluated in comparison with the veterinary high-definition oscillometry (HDO) in conscious normotensive dogs. Systolic and diastolic BPs were evaluated in two groups of dogs. The bias, the limits of agreement and correlation between variables were calculated. Twenty-five and 36 dogs were, respectively, included in Study No. 1 (dogs weighting ≥10 kg) and 2 (dogs weighting ≥20 kg). In both studies, correlation between the two devices was moderate. A better agreement was displayed for diastolic pressure and poor precision for both systolic and diastolic pressures measurements (as determined by wide limits of agreement). The WBP method underestimated both the systolic and diastolic BP with respect to the HDO method. The inclusion of bigger dogs (Study No. 2) with limb circumference more like to human limb dimension did not improve the agreement between considered methods. SIGNIFICANCE: The human WBP monitor considered is not suitable to replace the commonly used veterinary HDO for in-clinic BP monitoring in normotensive conscious dogs.

Polyethylene microplastics reduce filtration and respiration rates in the Mediterranean sponge Petrosia ficiformis.

Microplastic (MP) pollution represents a distinctive mark of the Anthropocene. Despite the increasing efforts to determine the ecological impacts of MP on marine biodiversity, our understanding of their toxicological effects on invertebrate species is still limited. Despite their key functional roles, sponges (Phylum Porifera) are particularly understudied in MP research. These filter-feeders extract and retain particles from the water column, across a broad size range. In this study, we carried out a laboratory experiment to assess the uptake of MPs (polyethylene, PE) by the Mediterranean sponge Petrosia ficiformis, how MPs influence key biological process after different times of exposure (24h and 72h) and whether they can be subsequently eliminated. MP uptake increased with time of exposure, with 30.6% of the inoculated MP particles found in sponge samples after 72h. MPs impaired filtration and respiration rates and these effects were still evident 72h after sponges had been transferred in uncontaminated water. Our study shows that time of exposure represents a key factor in determining MP toxicity in sponges. In addition, our results suggest that sponges are able to incorporate foreign particles and may thus be a potential bioindicator for MP pollutants.

Self-Assembled Amphiphilic Fluorinated Random Copolymers for the Encapsulation and Release of the Hydrophobic Combretastatin A-4 Drug.

Water-soluble amphiphilic random copolymers composed of tri(ethylene glycol) methacrylate (TEGMA) or poly(ethylene glycol) methyl ether methacrylate (PEGMA) and perfluorohexylethyl acrylate (FA) were synthesized by ARGET-ATRP, and their self-assembling and thermoresponsive behavior in water was studied by dynamic light scattering (DLS) and UV-vis spectroscopy. The copolymer ability to self-fold in single-chain nano-sized structures (unimer micelles) in aqueous solutions was exploited to encapsulate Combretastatin A-4 (CA-4), which is a very hydrophobic anticancer drug. The cloud point temperature (Tcp) was found to linearly decrease with increasing drug concentration in the drug/copolymer system. Moreover, while CA-4 was preferentially incorporated into the unimer micelles of TEGMA-ran-FA, the drug was found to induce multi-chain, submicro-sized aggregation of PEGMA-ran-FA. Anyway, the encapsulation efficiency was very high (≥81%) for both copolymers. The drug release was evaluated in PBS aqueous solutions both below and above Tcp for TEGMA-ran-FA copolymer and below Tcp, but at two different drug loadings, for PEGMA-ran-FA copolymer. In any case, the release kinetics presented similar profiles, characterized by linear trends up to ≈10-13 h and ≈7 h for TEGMA-ran-FA and PEGMA-ran-FA, respectively. Then, the release rate decreased, reaching a plateau. The release from TEGMA-ran-FA was moderately faster above Tcp than below Tcp, suggesting that copolymer thermoresponsiveness increased the release rate, which occurred anyway by diffusion below Tcp. Cytotoxicity tests were carried out on copolymer solutions in a wide concentration range (5-60 mg/mL) at 37 °C by using Balb/3T3 clone A31 cells. Interestingly, it was found that the concentration-dependent micro-sized aggregation of the amphiphilic random copolymers above Tcp caused a sort of "cellular asphyxiation" with a loss of cell viability clearly visible for TEGMA-ran-FA solutions (Tcp below 37 °C) with higher copolymer concentrations. On the other hand, cells in contact with the analogous PEGMA-ran-FA (Tcp above 37 °C) presented a very good viability (≥75%) with respect to the control at any given concentration.

VenomPred: A Machine Learning Based Platform for Molecular Toxicity Predictions.

The use of in silico toxicity prediction methods plays an important role in the selection of lead compounds and in ADMET studies since in vitro and in vivo methods are often limited by ethics, time, budget and other resources. In this context, we present our new web tool VenomPred, a user-friendly platform for evaluating the potential mutagenic, hepatotoxic, carcinogenic and estrogenic effects of small molecules. VenomPred platform employs several in-house Machine Learning (ML) models developed with datasets derived from VEGA QSAR, a software that includes a comprehensive collection of different toxicity models and has been used as a reference for building and evaluating our ML models. The results showed that our models achieved equal or better performance than those obtained with the reference models included in VEGA QSAR. In order to improve the predictive performance of our platform, we adopted a consensus approach combining the results of different ML models, which was able to predict chemical toxicity better than the single models. This improved method was thus implemented in the VenomPred platform, a freely accessible webserver that takes the SMILES (Simplified Molecular-Input Line-Entry System) strings of the compounds as input and sends the prediction results providing a probability score about their potential toxicity.

Dispersity within Brushes Plays a Major Role in Determining Their Interfacial Properties: The Case of Oligoxazoline-Based Graft Polymers.

Many synthetic polymers used to form polymer-brush films feature a main backbone with functional, oligomeric side chains. While the structure of such graft polymers mimics biomacromolecules to an extent, it lacks the monodispersity and structural purity present in nature. Here we demonstrate that side-chain heterogeneity within graft polymers significantly influences hydration and the occurrence of hydrophobic interactions in the subsequently formed brushes and consequently impacts fundamental interfacial properties. This is demonstrated for the case of poly(methacrylate)s (PMAs) presenting oligomeric side chains of different length (n) and dispersity. A precise tuning of brush structure was achieved by first synthesizing oligo(2-ethyl-2-oxazoline) methacrylates (OEOXMAs) by cationic ring-opening polymerization (CROP), subsequently purifying them into discrete macromonomers with distinct values of n by column chromatography, and finally obtaining poly[oligo(2-ethyl-2-oxazoline) methacrylate]s (POEOXMAs) by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Assembly of POEOXMA on Au surfaces yielded graft polymer brushes with different side-chain dispersities and lengths, whose properties were thoroughly investigated by a combination of variable angle spectroscopic ellipsometry (VASE), quartz crystal microbalance with dissipation (QCMD), and atomic force microscopy (AFM) methods. Side-chain dispersity, or dispersity within brushes, leads to assemblies that are more hydrated, less adhesive, and more lubricious and biopassive compared to analogous films obtained from graft polymers characterized by a homogeneous structure.

Amphiphilic Polyphosphonate Copolymers as New Additives for PDMS-Based Antifouling Coatings.

Poly(ethyl ethylene phosphonate)-based methacrylic copolymers containing polysiloxane methacrylate (SiMA) co-units are proposed as surface-active additives as alternative solutions to the more investigated polyzwitterionic and polyethylene glycol counterparts for the fabrication of novel PDMS-based coatings for marine antifouling applications. In particular, the same hydrophobic SiMA macromonomer was copolymerized with a methacrylate carrying a poly(ethyl ethylene phosphonate) (PEtEPMA), a phosphorylcholine (MPC), and a poly(ethylene glycol) (PEGMA) side chain to obtain non-water soluble copolymers with similar mole content of the different hydrophilic units. The hydrolysis of poly(ethyl ethylene phosphonate)-based polymers was also studied in conditions similar to those of the marine environment to investigate their potential as erodible films. Copolymers of the three classes were blended into a condensation cure PDMS matrix in two different loadings (10 and 20 wt%) to prepare the top-coat of three-layer films to be subjected to wettability analysis and bioassays with marine model organisms. Water contact angle measurements showed that all of the films underwent surface reconstruction upon prolonged immersion in water, becoming much more hydrophilic. Interestingly, the extent of surface modification appeared to be affected by the type of hydrophilic units, showing a tendency to increase according to the order PEGMA < MPC < PEtEPMA. Biological tests showed that Ficopomatus enigmaticus release was maximized on the most hydrophilic film containing 10 wt% of the PEtEP-based copolymer. Moreover, coatings with a 10 wt% loading of the copolymer performed better than those containing 20 wt% for the removal of both Ficopomatus and Navicula, independent from the copolymer nature.

Recent Advances in In Silico Target Fishing.

In silico target fishing, whose aim is to identify possible protein targets for a query molecule, is an emerging approach used in drug discovery due its wide variety of applications. This strategy allows the clarification of mechanism of action and biological activities of compounds whose target is still unknown. Moreover, target fishing can be employed for the identification of off targets of drug candidates, thus recognizing and preventing their possible adverse effects. For these reasons, target fishing has increasingly become a key approach for polypharmacology, drug repurposing, and the identification of new drug targets. While experimental target fishing can be lengthy and difficult to implement, due to the plethora of interactions that may occur for a single small-molecule with different protein targets, an in silico approach can be quicker, less expensive, more efficient for specific protein structures, and thus easier to employ. Moreover, the possibility to use it in combination with docking and virtual screening studies, as well as the increasing number of web-based tools that have been recently developed, make target fishing a more appealing method for drug discovery. It is especially worth underlining the increasing implementation of machine learning in this field, both as a main target fishing approach and as a further development of already applied strategies. This review reports on the main in silico target fishing strategies, belonging to both ligand-based and receptor-based approaches, developed and applied in the last years, with a particular attention to the different web tools freely accessible by the scientific community for performing target fishing studies.