Synthesis of platinum (II) N-heterocyclic carbenes based on adenosine

Funding Information: This research was funded by national funds through FCT?Funda??o para a Ci?ncia e a Tecnologia, I.P., Project MOSTMICRO-ITQB (refs. UIDB/04612/2020 and UIDP/04612/2020), and IF/00109/2014/CP1244/CT0007. This work was also supported by FCT fellowships number PD/BD/135483/2018 (M.I.P.S.L.) and SFRH/BD/1444412019 (G.F.). Clara S. B. Gomes acknowledges the Associate Laboratory for Green Chemistry?LAQV and the Applied Molecular Biosciences Unit?UCIBIO, which are financed by national funds from Funda??o para a Ci?ncia e a Tecnologia (UIDB/50006/2020, UIDP/50006/2020, UIDB/04378/2020, UIDP/04378/2020, respectively).The NMR spectra were acquired at CERMAX?ITQB, integrated in the National NMR Network and are partially supported by Infrastructure Project No. 022161 (co-financed by FEDER through COMPETE 2020, POCI, PORL and FCT through PIDDAC). Mass spectroscopy measurements were obtained by the UniMass Laboratory at ITQB-NOVA, Portugal. Clara S. B. Gomes acknowledges the XTAL?Macromolecular Crystallography group for granting access to the X-ray diffractometer. X-ray infrastructure financed by FCT-MCTES through project RECI/BBB-BEP/0124/2012. Funding Information: Funding: This research was funded by national funds through FCT—Fundação para a Ciência e a Tecnologia, I.P., Project MOSTMICRO-ITQB (refs. UIDB/04612/2020 and UIDP/04612/2020), and IF/00109/2014/CP1244/CT0007. This work was also supported by FCT fellowships number PD/BD/135483/2018 (M.I.P.S.L.) and SFRH/BD/1444412019 (G.F.). Clara S. B. Gomes acknowledges the Associate Laboratory for Green Chemistry—LAQV and the Applied Molecular Biosciences Unit—UCIBIO, which are financed by national funds from Fundação para a Ciência e a Tecnologia (UIDB/50006/2020, UIDP/50006/2020, UIDB/04378/2020, UIDP/04378/2020, respectively). Funding Information: Acknowledgments: The NMR spectra were acquired at CERMAX—ITQB, integrated in the National NMR Network and are partially supported by Infrastructure Project No. 022161 (co-financed by FEDER through COMPETE 2020, POCI, PORL and FCT through PIDDAC). Mass spectroscopy measurements were obtained by the UniMass Laboratory at ITQB-NOVA, Portugal. Clara S. B. Gomes acknowledges the XTAL—Macromolecular Crystallography group for granting access to the X-ray diffractometer. X-ray infrastructure financed by FCT-MCTES through project RECI/BBB-BEP/0124/2012. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.Organometallic derivatization of nucleosides is a highly promising strategy for the im-provement of the therapeutic profile of nucleosides. Herein, a methodology for the synthesis of metalated adenosine with a deprotected ribose moiety is described. Platinum (II) N-heterocyclic carbene complexes based on adenosine were synthesized, namely N-heterocyclic carbenes bearing a protected and unprotected ribose ring. Reaction of the 8-bromo-2′,3′,5′-tri-O-acetyladenosine with Pt (PPh3)4 by C8−Br oxidative addition yielded complex 1, with a PtII centre bonded to C-8 and an unprotonated N7. Complex 1 reacted at N7 with HBF4 or methyl iodide, yielding protic carbene 2 or methyl carbene 3, respectively. Deprotection of 1 to yield 4 was achieved with NH4OH. Deprotected compound 4 reacted at N7 with HCl solutions to yield protic NHC 5 or with methyl iodide yielding methyl carbene 6. Protic N-heterocyclic carbene 5 is not stable in DMSO solutions leading to the formation of compound 7, in which a bromide was replaced by chloride. The cis-influence of complexes 1–7 was examined by31P{1H} and195Pt NMR. Complexes 2, 3, 5, 6 and 7 induce a decrease of1 JPt,P of more than 300 Hz, as result of the higher cis-influence of the N-heterocyclic carbene when compared to the azolato ligand in 1 and 4.publishersversionpublishe

Benzo[a]phenoxazinium chlorides functionalized with chloride atoms and/or ester groups

Proceedings of the 19th Int. Electron. Conf. Synth. Org. Chem.With the aim of contributing to the development of fluorescent near-infrared (NIR) probes with applications in biomedicine, our research group is committed to the development of new water-soluble benzo[a]phenoxazine derivatives and the evaluation of their photophysical and biological potential. Herein we report the photophysical behaviour in anhydrous ethanol of four synthesised benzo[a]phenoxazinium chlorides, possessing the (3-chloropropyl)amino and/or (4-ethoxy-4- oxobutyl)amino groups at 5- and 9-positions of the polycyclic system.Thanks are due to the Fundação para a Ciência e Tecnologia (FCT, Portugal) for financial support to the NMR portuguese network (PTNMR, Bruker Avance III 400-Univ. Minho), FCT and FEDER (European Fund for Regional Development)-COMPETE-QREN-EU for financial support to the Research Centres CFUM [PEst-C/FIS/UI0607/2011 (F-COMP-01-0124-FEDER-022711)] and CQ/UM [PEstC/QUI/UI0686/2013(FCOMP-01-0124-FEDER-022716)]. A post-doctoral grant to B. R. Raju (SFRH/BPD/62881/2009) is also acknowledged to FCT, POPH-QREN, FSE.info:eu-repo/semantics/publishedVersio

Synthesis and photophysical studies of new benzo[a]phenoxazinium chlorides as potential antifungal agents

A set of four new benzo[a]phenoxazinium chlorides possessing ethyl, propyl, decyl and tetradecyl groups at the 9-amino function of the heterocycle along with a propyl group at the 5-amino position was efficiently synthesised. These compounds displayed fluorescence with maximum emission wavelengths of 673 and 685 nm, in anhydrous ethanol and water. All the benzo[a]phenoxazines were evaluated against the yeast Saccharomyces cerevisiae in a broth microdilution assay. It was found that their antifungal activity depended on the variation in the lengths of the aliphatic chains. The highest MIC activity of 1.56 µM was obtained for compound 7 comprising a di-alkylated propyl substituent at 9-amino position and a propyl chain at the 5-amino position of the heterocycle core.FEDER-COMPETE-QREN-EUFSEThanks are due to the Fundação para a Ciência e Tecnologia (FCT, Portugal) for financial support to the NMR portuguese network (PTNMR, Bruker Avance III 400-Univ. Minho), FCT and FEDER (European Fund for Regional Development)-COMPETE-QREN-EU for financial support to the Research Centres CFUM [PEst-C/FIS/UI0607/2011 (F-COMP-01-0124-FEDER-022711)] and CQ/UM [PEst-C/QUI/UI0686/2011 (FCOMP-01-0124-FEDER-022716)]. A post-doctoral grant to B. R. Raju (SFRH/BPD/62881/2009) is also acknowledged to FCT, POPH-QREN, FSE. This work was supported by the strategic programme UID/BIA/04050/2013 (POCI-01- 0145-FEDER-007569) funded by national funds through the FCT I.P. and by the ERDF through the COMPETE2020 - Programa Operacional Competitividade e Internacionalização (POCI).ERDFPOPH-QRENCOMPETE202

New benzo[a]phenoxazines bearing the (4,6-dichloro-1,3,5-triazin-2-yl)amino group: synthesis and photophysical properties

Synthesis of new benzo[a]phenoxazinium chlorides possessing the (4,6-dichloro-1,3,5- triazin-2-yl)amino at 5-amino function of the heterocycles is described. The preliminary photophysical properties of these compounds in anhydrous ethanol when acidified with TFA or basified with TEAH is also investigated, as well as their response in aqueous media. These benzo[a]phenoxazinium chlorides exhibited fluorescence with maximum emission wavelengths between 628 and 676 nm, in anhydrous ethanol and water.Thanks are due to the Fundação para a Ciência e Tecnologia (FCT, Portugal) for financial support to the NMR portuguese network (PTNMR, Bruker Avance III 400-Univ. Minho), FCT and FEDER (European Fund for Regional Development)-COMPETE-QREN-EU for financial support to the Research Centres CFUM [PEst-C/FIS/UI0607/2011 (F-COMP-01-0124-FEDER-022711)] and CQ/UM [PEst-C/QUI/UI0686/2013(FCOMP-01-0124-FEDER-022716)]. A post-doctoral grant to B. R. Raju (SFRH/BPD/62881/2009) is also acknowledged to FCT, POPH-QREN, FSE.info:eu-repo/semantics/publishedVersio

Tuning the Biological Activity of Camphorimine Complexes through Metal Selection

This research was funded by FCT—Fundação para a Ciência e a Tecnologia, through projects CQE (UIDB/00100/2020 and UIDP/00100/2020) and C2TN (UID/MULTI/04349/2019), the projects of the Research Unit Institute for Bioengineering and Biosciences—iBB (UIDB/04565/2020 and UIDP/04565/2020), the project LA/P/0140/2020 of the Associate Laboratory Institute for Health and Bioeconomy—i4HB, and a PhD grant to J.P.C. (UI/BD/152244/2021).The cytotoxic activity of four sets of camphorimine complexes based on the Cu(I), Cu(II), Ag(I), and Au(I) metal sites were assessed against the cisplatin-sensitive A2780 and OVCAR3 ovarian cancer cells. The results showed that the gold complexes were ca. one order of magnitude more active than the silver complexes, which in turn were ca. one order of magnitude more active than the copper complexes. An important finding was that the cytotoxic activity of the Ag(I) and Au(I) camphorimine complexes was higher than that of cisplatin. Another relevant aspect was that the camphorimine complexes did not interact significantly with DNA, in contrast with cisplatin. The cytotoxic activity of the camphorimine complexes displayed a direct relationship with the cellular uptake by OVCAR3 cells, as ascertained by PIXE (particle-induced X-ray emission). The levels of ROS (reactive oxygen species) formation exhibited an inverse relationship with the reduction potentials for the complexes with the same metal, as assessed by cyclic voltammetry. In order to gain insight into the toxicity of the complexes, their cytotoxicity toward nontumoral cells (HDF and V79 fibroblasts) was evaluated. The in vivo cytotoxicity of complex 5 using the nematode Caenorhabditis elegans was also assessed. The silver camphorimine complexes displayed the highest selectivity coefficients (activity vs. toxicity).publishersversionpublishe

A comprehensive assessment of the transcriptome of cork oak (Quercus suber) through EST sequencing

Background: Cork oak (Quercus suber) is one of the rare trees with the ability to produce cork, a material widely used to make wine bottle stoppers, flooring and insulation materials, among many other uses. The molecular mechanisms of cork formation are still poorly understood, in great part due to the difficulty in studying a species with a long life-cycle and for which there is scarce molecular/genomic information. Cork oak forests are of great ecological importance and represent a major economic and social resource in Southern Europe and Northern Africa. However, global warming is threatening the cork oak forests by imposing thermal, hydric and many types of novel biotic stresses. Despite the economic and social value of the Q. suber species, few genomic resources have been developed, useful for biotechnological applications and improved forest management. Results: We generated in excess of 7 million sequence reads, by pyrosequencing 21 normalized cDNA libraries derived from multiple Q. suber tissues and organs, developmental stages and physiological conditions. We deployed a stringent sequence processing and assembly pipeline that resulted in the identification of ~159,000 unigenes. These were annotated according to their similarity to known plant genes, to known Interpro domains, GO classes and E.C. numbers. The phylogenetic extent of this ESTs set was investigated, and we found that cork oak revealed a significant new gene space that is not covered by other model species or EST sequencing projects. The raw data, as well as the full annotated assembly, are now available to the community in a dedicated web portal at http://www.corkoakdb.org. Conclusions: This genomic resource represents the first trancriptome study in a cork producing species. It can be explored to develop new tools and approaches to understand stress responses and developmental processes in forest trees, as well as the molecular cascades underlying cork differentiation and disease response.Peer Reviewe

Characterization of the cork oak transcriptome dynamics during acorn development

Background: Cork oak (Quercus suber L.) has a natural distribution across western Mediterranean regions and is a keystone forest tree species in these ecosystems. The fruiting phase is especially critical for its regeneration but the molecular mechanisms underlying the biochemical and physiological changes during cork oak acorn development are poorly understood. In this study, the transcriptome of the cork oak acorn, including the seed, was characterized in five stages of development, from early development to acorn maturation, to identify the dominant processes in each stage and reveal transcripts with important functions in gene expression regulation and response to water. Results: A total of 80,357 expressed sequence tags (ESTs) were de novo assembled from RNA-Seq libraries representative of the several acorn developmental stages. Approximately 7.6 % of the total number of transcripts present in Q. suber transcriptome was identified as acorn specific. The analysis of expression profiles during development returned 2,285 differentially expressed (DE) transcripts, which were clustered into six groups. The stage of development corresponding to the mature acorn exhibited an expression profile markedly different from other stages. Approximately 22 % of the DE transcripts putatively code for transcription factors (TF) or transcriptional regulators, and were found almost equally distributed among the several expression profile clusters, highlighting their major roles in controlling the whole developmental process. On the other hand, carbohydrate metabolism, the biological pathway most represented during acorn development, was especially prevalent in mid to late stages as evidenced by enrichment analysis. We further show that genes related to response to water, water deprivation and transport were mostly represented during the early (S2) and the last stage (S8) of acorn development, when tolerance to water desiccation is possibly critical for acorn viability. Conclusions: To our knowledge this work represents the first report of acorn development transcriptomics in oaks. The obtained results provide novel insights into the developmental biology of cork oak acorns, highlighting transcripts putatively involved in the regulation of the gene expression program and in specific processes likely essential for adaptation. It is expected that this knowledge can be transferred to other oak species of great ecological value.Fundação para a Ciência e a Tecnologi

MAMMALS IN PORTUGAL : A data set of terrestrial, volant, and marine mammal occurrences in P ortugal

Mammals are threatened worldwide, with 26% of all species being includedin the IUCN threatened categories. This overall pattern is primarily associatedwith habitat loss or degradation, and human persecution for terrestrial mam-mals, and pollution, open net fishing, climate change, and prey depletion formarine mammals. Mammals play a key role in maintaining ecosystems func-tionality and resilience, and therefore information on their distribution is cru-cial to delineate and support conservation actions. MAMMALS INPORTUGAL is a publicly available data set compiling unpublishedgeoreferenced occurrence records of 92 terrestrial, volant, and marine mam-mals in mainland Portugal and archipelagos of the Azores and Madeira thatincludes 105,026 data entries between 1873 and 2021 (72% of the data occur-ring in 2000 and 2021). The methods used to collect the data were: live obser-vations/captures (43%), sign surveys (35%), camera trapping (16%),bioacoustics surveys (4%) and radiotracking, and inquiries that represent lessthan 1% of the records. The data set includes 13 types of records: (1) burrowsjsoil moundsjtunnel, (2) capture, (3) colony, (4) dead animaljhairjskullsjjaws, (5) genetic confirmation, (6) inquiries, (7) observation of live animal (8),observation in shelters, (9) photo trappingjvideo, (10) predators dietjpelletsjpine cones/nuts, (11) scatjtrackjditch, (12) telemetry and (13) vocalizationjecholocation. The spatial uncertainty of most records ranges between 0 and100 m (76%). Rodentia (n=31,573) has the highest number of records followedby Chiroptera (n=18,857), Carnivora (n=18,594), Lagomorpha (n=17,496),Cetartiodactyla (n=11,568) and Eulipotyphla (n=7008). The data setincludes records of species classified by the IUCN as threatened(e.g.,Oryctolagus cuniculus[n=12,159],Monachus monachus[n=1,512],andLynx pardinus[n=197]). We believe that this data set may stimulate thepublication of other European countries data sets that would certainly contrib-ute to ecology and conservation-related research, and therefore assisting onthe development of more accurate and tailored conservation managementstrategies for each species. There are no copyright restrictions; please cite thisdata paper when the data are used in publications.info:eu-repo/semantics/publishedVersio

Pervasive gaps in Amazonian ecological research

Biodiversity loss is one of the main challenges of our time,1,2 and attempts to address it require a clear un derstanding of how ecological communities respond to environmental change across time and space.3,4 While the increasing availability of global databases on ecological communities has advanced our knowledge of biodiversity sensitivity to environmental changes,5–7 vast areas of the tropics remain understudied.8–11 In the American tropics, Amazonia stands out as the world’s most diverse rainforest and the primary source of Neotropical biodiversity,12 but it remains among the least known forests in America and is often underrepre sented in biodiversity databases.13–15 To worsen this situation, human-induced modifications16,17 may elim inate pieces of the Amazon’s biodiversity puzzle before we can use them to understand how ecological com munities are responding. To increase generalization and applicability of biodiversity knowledge,18,19 it is thus crucial to reduce biases in ecological research, particularly in regions projected to face the most pronounced environmental changes. We integrate ecological community metadata of 7,694 sampling sites for multiple or ganism groups in a machine learning model framework to map the research probability across the Brazilian Amazonia, while identifying the region’s vulnerability to environmental change. 15%–18% of the most ne glected areas in ecological research are expected to experience severe climate or land use changes by 2050. This means that unless we take immediate action, we will not be able to establish their current status, much less monitor how it is changing and what is being lostinfo:eu-repo/semantics/publishedVersio