Impacts of climate change on mangrove subsistence fisheries: a global review.

Unlabelled: Climate change will impact coastal ecosystems, threatening subsistence fisheries including those in mangrove forests. Despite their global contributions and roles in nutrition and cultural identity, mangrove subsistence fisheries are poorly studied. Here, we offer a foundation for improving the management of mangrove subsistence fisheries to deal with the impending effects of climate change.

Patient-related risk factors for early unplanned reoperation following revision total shoulder arthroplasty.

Purpose: There has been an increase in the number of total shoulder arthroplasty (TSA) revisions performed as the number of primary surgeries increases rapidly. Revision procedures have a higher failure rate and there is a lack of understanding of patient risk factors for needing another repeat surgery following revision TSA.

Methods: Revision patients were separated into two cohorts: those needing an unplanned reoperation and those that did not within 30 days following revision TSA.

Rhenium(I) and technetium(I) complexes with megazol derivatives: towards the development of a theranostic platform for Chagas disease.

The diagnosis and treatment of Chagas disease (CD) in the chronic phase remains a challenge. With that in mind, a potential theranostic device based on the trypanocidal agent known as megazol and the -M(CO) (M = Re or Tc) fragment is proposed in the present work. The peripheral structure of megazol (L) was modified to obtain the compounds L (R1 = H, R2 = Me and R1 = R2 = Me), which were used in the syntheses of complexes of composition [ReBr(CO)L].

Synthesis, Characterization, and Biological Evaluation of Novel [M(η-arene)] (M = Re, Tc) Hosted Terpyridines and Copper Complexes Thereof.

We report the synthesis, characterization, and in vitro biological activities of [Re(η-arene)]-terpyridine conjugates and their Cu complexes. The terpyridine (terpy) chelators were attached to the [Re(η-arene)] scaffold via secondary amine linkers allowing for heteroleptic mono- and homoleptic bis-terpyridine-substituted chelators. Complexation with CuCl afforded the respective square pyramidal [Cu(terpy)Cl] complexes hosted on the [Re(η-arene)] scaffold.

Direct Anchoring of Molybdenum Sulfide Molecular Catalysts on Antimony Selenide Photocathodes for Solar Hydrogen Production.

Molybdenum sulfide serves as an effective nonprecious metal catalyst for hydrogen evolution, primarily active at edge sites with unsaturated molybdenum sites or terminal disulfides. To improve the activity at a low loading density, two molybdenum sulfide clusters, [MoS] and [MoS], were investigated. The MoS molecular catalysts were heterogenized on SbSe with a simple soaking treatment, resulting in a thin catalyst layer of only a few nanometers that gave up to 20 mA cm under one sun illumination.

Evaluation of somatic copy number variation detection by NGS technologies and bioinformatics tools on a hyper-diploid cancer genome.

Background: Copy number variation (CNV) is a key genetic characteristic for cancer diagnostics and can be used as a biomarker for the selection of therapeutic treatments. Using data sets established in our previous study, we benchmark the performance of cancer CNV calling by six most recent and commonly used software tools on their detection accuracy, sensitivity, and reproducibility. In comparison to other orthogonal methods, such as microarray and Bionano, we also explore the consistency of CNV calling across different technologies on a challenging genome.

CO-INFECTION OF DENGUE AND HEPATITIS A VIRUSES: A RARE CASE REPORT.

Dengue fever and hepatitis A are endemic infections caused by viruses that mostly affect developing countries (Volchkova , 2016). Co-infection is rare, and represents a diagnostic challenge due to their overlapping symptoms (Yakoob , 2009). The febrile syndrome accompanied by abdominal pain and vomiting are the common clinical manifestations of both pathologies.

Does deep TMS really works for smoking cessation? A prospective, double blind, randomized, sham controlled study.

Introduction: A substantial proportion of smokers wishing to quit do not stop smoking when using current therapies to aid cessation. Magnetic pulses to specific brain areas designated as transcranial magnetic stimulation may modulate brain activity and thereby change chemical dependencies. Deep transcranial magnetic stimulation (dTMS) with the H4 coil stimulates neuronal pathways in the lateral prefrontal cortex and insula bilaterally, areas involved in tobacco addiction.

Light-Driven Ring Slippage in [Re(η-CH)(η-CH)] and the Inertness of Its Technetium Homologue.

Here, we present the light-driven reactions of [Re(η-CH)(η-CH)] () with nitriles, phosphines, and isocyanides, which are added to via a ring slippage of the tropylium cation from η to η, forming [Re(η-CH)(η-CH)(L)] (L= acetonitrile ; 2-phenylacetonitrile ; 1,3,5-triaza-5-phosphoadamantane (PTA) ; -butyl isocyanide ; benzyl isocyanide ) and [Re(η-CH)(η-CH)(L)] with L = (ethane-1,2-diyl)bis(diphenylphosphane) (dppe) . To compare the reactivities of rhenium and technetium, we also investigated the synthesis of [Tc(η-CH)], its substitution of naphthalene with cyclohepta-1,3,5-triene to obtain [Tc(η-CH)(η-CH)], and its reactivity (or lack thereof) with light.

Induced - rearrangements in {M(CO)} complexes (M = Re, Tc) by a PNP ligand.

The - rearrangements in [MX(CO)] (M = Re, Tc) induced by a pincer-type ligand (PNP) and a "halide scavenger" are reported. The reactions of -[Tc(CO)(OH)] or [TcO] in saline both yield -[Tc(PNP)(CO)], the first example of a -{Tc(CO)} type complex. In contrast, reactions with terpyridine (terpy) only gave the facial κ-terpy complexes with Re and Tc.

and studies of [M(η-pseudoerlotinib)] sandwich complexes (M = Re, Tc).

The pursuit of molecular imaging for tumors has led to endeavors focused on targeting epidermal growth factor receptors (EGFR) through monoclonal antibodies or radionuclide-labelled EGF analogs with Tc, In, or I. In this context, various Tc-labeled EGFR inhibitors using quinazoline structures have been reported based on the so-called pendant approach and on two types of complexes and labelling strategies: "4 + 1" mixed ligand complexes and -tricarbonyl complexes. Apart from this approach, which alters lead structures by linking pharmacophores to chelator frameworks through different connectors, the integrated incorporation of topoisomerase and tyrosine kinase inhibitors into Re and Tc complexes has not been explored.

Role of Pure Technetium Chemistry: Are There Still Links to Applications in Imaging?

The discovery and development of new Tc-based radiopharmaceuticals or labeled drugs in general is based on innovative, pure chemistry and subsequent, application-targeted research. This was the case for all currently clinically applied imaging agents. Most of them were market-introduced some 20 years ago, and the few more recent ones are based on even older chemistry, albeit technetium chemistry has made substantial progress over the last 20 years.

Binding Small Molecules to a -Dicarbonyl Tc-PNP Complex via Metal-Ligand Cooperativity.

Metal-ligand cooperativity is a powerful tool for the activation of various bonds but has rarely, if ever, been studied with the radioactive transition metal Tc. In this work, we explore this bond activation pathway with the dearomatized PNP complex -[Tc(PNP*)(CO)] (), which was synthesized by deprotonation of -[Tc(PNP)(CO)Cl] with KOBu. Analogous to its rhenium congener, the dearomatized compound reacts with CO to form the carboxy complex -[Tc(PNP-COO)(CO)] and with H to form the mono-hydride complex -[Tc(PNP)(CO)H] ().

Exploring Rhenium Arene Piano-Stool Chemistry with [Re(η-CH)(NCCH)]: A Powerful Semi-Solvated Precursor.

Thermal treatment of the Re hydride complex [ReH(η-CH)(η-CH)] in CHCN results in the formation of [Re(η-CH)(NCCH)]. This semi-solvated complex is remarkably stable under an ambient atmosphere and exhibits a fast CHCN self-exchange, which facilitates substitution reactions. The CHCN ligands are replaced by σ-donating phosphines such as trimethyl phosphine (PMe), triphenyl phosphine (PPh), or the bidentate 1,2-bis(diphenylphosphino)ethane (dppe) to afford [Re(η-CH)(NCCH)(PR)] (if R = Me, then = 2; if R = Ph, then = 1 or 2) or [Re(η-CH)(dppe)(NCCH)], respectively.

One Electron Changes Everything: Synthesis, Characterization, and Reactivity Studies of [Re(NCCH)].

Oxidation of [Re(NCCH)] with the thianthrene radical cation results in the formation of [Re(NCCH)], one of the very rare cases of a fully solvated +3 complex. It was fully characterized by spectroscopy and X-ray structure analysis. In contrast to its reduced analogue, [Re(NCCH)] exhibits a much faster CHCN exchange.

High-Yield Tc Labeling of Gold Nanoparticles Carrying Atropine and Adrenaline.

This work focuses on the synthesis, purification, and analytical characterization of novel multifunctional Au NPs radiolabeled with Tc. These mixed-ligand shell Au NPs represent pharmacologically relevant samples for potential application in theragnostics. A ligand using a plain linker with a rather long chain consisting of 10 CH groups and a thiol moiety along with the PADA chelator has been used for both the attachment to the Au NP surface and for the Tc(CO) complexation.

Two Novel Dinuclear Cobalt Polypyridyl Complexes in Electro- and Photocatalysis for Hydrogen Production: Cooperativity Increases Performance.

Syntheses and mechanisms of two dinuclear Co-polypyridyl catalysts for the H evolution reaction (HER) were reported and compared to their mononuclear analogue (R1). In both catalysts, two di-(2,2'-bipyridin-6-yl)-methanone units were linked by either 2,2'-bipyridin-6,6'-yl or pyrazin-2,5-yl. Complexation with Co gave dinuclear compounds bridged by pyrazine (C2) or bipyridine (C1).

An isoindoline bridged [M(η-arene)] (M = Re, Tc) -arenophane and its dinuclear macrocycles with axial chirality.

This work presents a straightforward method for the preparation of an isoindoline bridged [M(arene)] (M = Re, Tc) -[3]arenophane. This intramolecular formation of an -complex is accompanied by the intermolecular formation of a pair of isoindoline bridged macrocyclic dinuclear sandwich complexes, one of which exhibits axial chirality.

Watching Hydrogens Migrate: Step by Step from [Re(η-CH)] to [Re(η-CH)(η-CH)(NCCH)].

Arene substitution reactions in [M(η-arene)] are well documented for Groups 6 and 8 but are essentially unknown for the manganese triad. Aiming to replace benzene in [Re(η-CH)], we altered the hapticity of one coordinated benzene, which we found to be tunable stepwise from an η to an η-allyl coordination mode. Reduction of [Re(η-CH)] with hydrides gives [Re(η-CH)(η-CH)].

Excited-state structure of copper phenanthroline-based photosensitizers.

Cu diimine complexes present a noble metal free alternative to classical Ru, Re, Ir and Pt based photosensitizers in solution photochemistry, photoelectrochemical or dye-sensitized solar cells. Optimization of these dyes requires understanding of factors governing the key photochemical properties: excited state lifetime and emission quantum yield. The involvement of exciplex formation in the deactivation of the photoexcited state is a key question.

Naphthalene Exchange in [Re(η -napht) ] with Pharmaceuticals Leads to Highly Functionalized Sandwich Complexes [M(η -pharm) ] (M=Re/ Tc).

Bis-arene sandwich complexes are generally prepared by the Fischer-Hafner reaction, which conditions are incompatible with most O- and N- functional groups. We report a new way for the synthesis of sandwich type complexes [Re(η -arene) ] and [Re(η -arene)(η -benzene)] from [Re(η -napht) ] and [Re(η -napht)(η -benzene)] , with functionalized arenes and pharmaceuticals. N-methylpyrrolidine (NMP) facilitates the substitution of naphthalene with the incoming arene.

Organometallic small molecule kinase inhibitors - direct incorporation of Re and 99mTc into Opaganib®.

[(η5-Cp)Re(CO)] was incorporated into the kinase inhibitor Opaganib®. The resulting bioorganometallic complex showed a similar anti-cancer activity to Opaganib® against PC-3 cancer cells. The IC value for the kinase SK2 is 30x higher than that of Opaganib®.

New approach for the synthesis of water soluble -[M(CO)] bis(diarylphosphino)alkylamine complexes (M = Tc, Re).

A novel proof-of-concept is reported to modify the water solubility and potential biological effects of a bis(diphenylphosphino)alkylamine (PNP) ligand and the corresponding metal complex, by introducing an amine group on the outer periphery of the pendant ligand arm. Thus, a tertiary butoxycarbonyl protected '-Boc-ethylenediamine-,-bis(diphenylphosphino) ('-Boc-PNP) ligand (1) was synthesized by reacting the protected ethylenediamine and chlorodiphenylphosphine in a 1 : 2 molar ratio. The corresponding -[Re(CO)('-Boc-PNP)Br] (1A) complex was then obtained by reacting '-Boc-PNP (1) with (EtN)-[Re(CO)Br] in equimolar amounts in DCM at 50 °C.