A carboxyl-functionalized covalent organic polymer for the efficient adsorption of saxitoxin

Saxitoxin (STX), the most widely distributed neurotoxin in marine waters and emerging cyanotoxin of concern in freshwaters, causes paralytic shellfish poisoning in humans upon consumption of contaminated shellfish. To allow for the efficient monitoring of this biotoxin, it is of high importance to find high-affinity materials for its adsorption. Herein, we report the design and synthesis of a covalent organic polymer for the efficient adsorption of STX. Two β-keto-enamine-based materials were prepared by self-assembly of 2,4,6-triformylphloroglucinol (Tp) with 2,5-diaminobenzoic acid (Pa-COOH) to give TpPa-COOH and with 2,5-diaminotoluene (Pa-CH3) to give TpPa-CH3. The carboxylic acid functionalized TpPa-COOH outperformed the methyl-bearing counterpart TpPa-CH3 by an order of magnitude despite the higher long-range order and surface area of the latter. The adsorption of STX by TpPa-COOH was fast with equilibrium reached within 1 h, and the Langmuir adsorption model gave a calculated maximum adsorption capacity, Qm, of 5.69 mg g-1, making this material the best reported adsorbent for this toxin. More importantly, the prepared TpPa-COOH also showed good reusability and high recovery rates for STX in natural freshwater, thereby highlighting the material as a good candidate for the extraction and pre-concentration of STX from aquatic environments.publishe

Adsorption of marine phycotoxin okadaic acid on a covalent organic framework

Phycotoxins, compounds produced by some marine microalgal species, can reach high concentrations in the sea when a massive proliferation occurs, the so-called harmful algal bloom. These compounds are especially dangerous to human health when concentrated in the digestive glands of seafood. In order to generate an early warning system to alert for approaching toxic outbreaks, it is very important to improve monitoring methods of phycotoxins in aquatic ecosystems. Solid-phase adsorption toxin tracking devices reported thus far based on polymeric resins have not been able to provide an efficient harmful algal bloom prediction system due to their low adsorption capabilities. In this work, a water-stable covalent organic framework (COF) was evaluated as adsorbent for the hydrophobic toxin okadaic acid, one of the most relevant marine toxins and the parental compound of the most common group of toxins responsible for the diarrhetic shellfish poisoning. Adsorption kinetics of okadaic acid onto the COF in seawater showed that equilibrium concentration was reached in only 60 min, with a maximum experimental adsorption of 61 mg g1. Desorption of okadaic acid from the COF was successful with both 70% ethanol and acetonitrile as solvent, and the COF material could be reused with minor losses in adsorption capacity for three cycles. The results demonstrate that COF materials are promising candidates for solid-phase adsorption in water monitoring devices.This article is a result of the project Nanotechnology Based Functional Solutions (NORTE-01-0145-FEDER-000019), supported by Norte Portugal Regional Operational Programme (NORTE2020) under the PORTUGAL 2020 Partnership Agreement through the European Regional Development Fund (ERDF). This project has received funding from the European Union’s Seventh Framework Programme for research, technological development and demonstration under grant agreement no. 600375.info:eu-repo/semantics/publishedVersio

Prognostic factors for patients treated with abiraterone

© Cecilia Melo Alvim. This work is licensed under the Creative Commons Attribution4.0 License. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/Aim: To evaluate prostate-specific antigen response (PSAr) defined as a ≥50% decrease in PSA concentration from the pretreatment value, as a prognostic factor in patients with metastatic castration-resistant prostate cancer (mCRPC) treated with abiraterone acetate (AA). Methods: Retrospective evaluation of patients with mCRPC treated with AA. Results: 124 patients were identified. Median overall survival and progression-free survival for patients achieving PSAr versus patients without PSAr were 29.3 versus 9.7 months and 17.0 versus 5.2 months, respectively. Multivariate analysis confirmed that PSAr correlated with better overall survival (hazard ratio: 0.19; 95% CI: 0.10-0.38; p < 0.001) and progression-free survival (hazard ratio: 0.24; 95% CI: 0.14-0.41; p < 0.001). Conclusion: PSAr can be utilized as prognostic and predictive factors in mCRPC patients treated with AA.info:eu-repo/semantics/publishedVersio

Building blocks and COFs formed in concert —Three‐component synthesis of pyrene‐fused Azaacene covalent organic framework in the bulk and as films

A three‐component synthesis methodology is described for the formation of covalent organic frameworks (COFs) containing extended aromatics. Notably, this approach enables synthesis of the building blocks and COF along parallel reaction landscapes, on a similar timeframe. The use of fragmental building block components, namely pyrene dione diboronic acid as aggregation‐inducing COF precursor and the diamines o‐phenylenediamine (Ph), 2,3‐diaminonaphthalene (Naph), or (1R,2R)‐(+)‐1,2‐diphenylethylenediamine (2Ph) as extending functionalization units in conjunction with 2,3,6,7,10,11‐hexahydroxytriphenylene, resulted in the formation of the corresponding pyrene‐fused azaacene, i.e., Aza‐COF series with full conversion of the dione moiety, long‐range order, and high surface area. In addition, the novel three‐component synthesis was successfully applied to produce highly crystalline, oriented thin films of the Aza‐COFs with nanostructured surfaces on various substrates. The Aza‐COFs exhibit light absorption maxima in the blue spectral region, and each Aza‐COF presents a distinct photoluminescence profile. Transient absorption measurements of Aza‐Ph‐ and Aza‐Naph‐COFs suggest ultrafast relaxation dynamics of excited‐states within these COFs.Deutsche Forschungsgemeinschaft | Ref. ME 4515/1-2Fundação para a Ciência e a Tecnologia | Ref. SFRH/BD/141865/2018Fundação para a Ciência e a Tecnologia | Ref. PTDC/QUI-OUT/2095/2021Fundação para a Ciência e a Tecnologia | Ref. UIDB/50011/2020Fundação para a Ciência e a Tecnologia | Ref. UIDP/50011/2020Fundação para a Ciência e a Tecnologia | Ref. LA/P/0006/2020National Science Foundation (EE.UU.) | Ref. DMR-1848067Engineering and Physical Sciences Research Council (Reino Unido) | Ref. EP/V055127/1Agencia Estatal de Investigación | Ref. RYC2020-030414-IUniversidade de Vigo/CISU

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

Mammals in Portugal: a data set of terrestrial, volant, and marine mammal occurrences in Portugal

Mammals are threatened worldwide, with ~26% of all species being included in the IUCN threatened categories. This overall pattern is primarily associated with habitat loss or degradation, and human persecution for terrestrial mammals, and pollution, open net fishing, climate change, and prey depletion for marine mammals. Mammals play a key role in maintaining ecosystems functionality and resilience, and therefore information on their distribution is crucial to delineate and support conservation actions. MAMMALS IN PORTUGAL is a publicly available data set compiling unpublished georeferenced occurrence records of 92 terrestrial, volant, and marine mammals in mainland Portugal and archipelagos of the Azores and Madeira that includes 105,026 data entries between 1873 and 2021 (72% of the data occurring in 2000 and 2021). The methods used to collect the data were: live observations/captures (43%), sign surveys (35%), camera trapping (16%), bioacoustics surveys (4%) and radiotracking, and inquiries that represent less than 1% of the records. The data set includes 13 types of records: (1) burrows | soil mounds | tunnel, (2) capture, (3) colony, (4) dead animal | hair | skulls | jaws, (5) genetic confirmation, (6) inquiries, (7) observation of live animal (8), observation in shelters, (9) photo trapping | video, (10) predators diet | pellets | pine cones/nuts, (11) scat | track | ditch, (12) telemetry and (13) vocalization | echolocation. The spatial uncertainty of most records ranges between 0 and 100 m (76%). Rodentia (n =31,573) has the highest number of records followed by Chiroptera (n = 18,857), Carnivora (n = 18,594), Lagomorpha (n = 17,496), Cetartiodactyla (n = 11,568) and Eulipotyphla (n = 7008). The data set includes records of species classified by the IUCN as threatened (e.g., Oryctolagus cuniculus [n = 12,159], Monachus monachus [n = 1,512], and Lynx pardinus [n = 197]). We believe that this data set may stimulate the publication of other European countries data sets that would certainly contribute to ecology and conservation-related research, and therefore assisting on the development of more accurate and tailored conservation management strategies for each species. There are no copyright restrictions; please cite this data paper when the data are used in publications

Extraction of Ibuprofen from Natural Waters Using a Covalent Organic Framework

Ibuprofen is one of the most widely used pharmaceuticals, and due to its inefficient removal by conventional wastewater treatment, it can be found in natural surface waters at high concentrations. Recently, we demonstrated that the TpBD-(CF3)2 covalent organic framework (COF) can adsorb ibuprofen from ultrapure water with high efficiency. Here, we investigate the performance of the COF for the extraction of ibuprofen from natural water samples from a lake, river, and estuary. In general, the complexity of the natural water matrix induced a reduction in the adsorption efficiency of ibuprofen as compared to ultrapure water. The best performance, with over 70% adsorption efficiency, was found in lake water, the sample which featured the lowest pH. According to the theoretical calculations, ibuprofen more favorably interacts with the COF pores in the protonated form, which could partially account for the enhanced adsorption efficiency found in lake water. In addition, we explored the effect of the presence of competing pharmaceuticals, namely, acetaminophen and phenobarbital, on the ibuprofen adsorption as binary mixtures. Acetaminophen and phenobarbital were adsorbed by TpBD-(CF3)2 with low efficiency and their presence led to an increase in ibuprofen adsorption in the binary mixtures. Overall, this study demonstrates that TpBD-(CF3)2 is an efficient adsorbent for the extraction of ibuprofen from natural waters as well

Novel imidazole-based hydrazonoyl cyanides and amidrazones containing N(N,O)-heterocycles: selective synthesis, reaction mechanisms and preliminary anticancer evaluation

Two series of novel hybrid heterocyclic compounds that combine the imidazole ring with bioactive piperidine, morpholine or piperazine heterosystems, through a hydrazone unit, were easily obtained by two competitive pathways. Starting from 5-amino-4-cyanoformimidoyl imidazoles and 1-aminopiperidine, 4-aminomorpholine or 1-amino-4-methylpiperazine under mild acidic media led to the selective synthesis of 5-aminoimidazole 4-carboxamidrazones, whereas the corresponding 4-hydrazonoyl cyanide derivatives were obtained under stronger acidic conditions. These highly functionalized imidazoles provide convenient synthetic precursors to a vast array of heterocycles with potential pharmaceutical applications. The reaction mechanisms were elucidated on the basis of experimental assays and in silico calculations. The compounds were screened against colorectal cancer HCT116-p53 wt cell line, and significant IC50 values of 3.69 µM and 4.83 µM were obtained.This research was funded by the Foundation for Science and Technology (FCT) through financial support to CQUM-Chemistry Centre of University of Minho (UID/QUI/00686/2020). Thanks are also due to FCT for financial support to the Portuguese NMR Network (PT NMR, Bruker Avance III 400-Univ. Minho).info:eu-repo/semantics/publishedVersio

Interface Engineering in Nanostructured Nickel Phosphide for Efficient and Stable Water Oxidation

An approach to significantly enhance the performance of the cost-effective nickel phosphide catalyst for electrochemical water oxidation has been developed via interfacing with Mg oxide-hydroxide. We have synthesized Ni2P nanoparticles anchored on Mg2O(OH)2-like phase supported on carbon paper. During the oxygen evolution reaction, the well-defined Ni2P nanoparticles serve as precursors for the immediate formation of active and stable nanostructured nickel hydroxide catalyst. As the anode for the oxygen evolution reaction in an alkaline electrolyte, the electrode shows a modest Tafel slope of 48 mV dec–1 and a large turnover frequency of 0.05 s–1 at an overpotential of 0.4 V. Microstructure and composition studies of the catalyst suggest that interfacial strain between Mg- and Ni-containing phases is responsible for high catalytic activity. A significant increase in catalytic activity upon the combination of magnesium compound and transition-metal phosphide suggests an interesting strategy for the controlled and reproducible preparation of active Earth-abundant oxygen-evolving catalysts