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1.
BMC Plant Biol ; 24(1): 238, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38566027

RESUMO

BACKGROUND: The fruity aromatic bouquet of coffee has attracted recent interest to differentiate high value market produce as specialty coffee. Although the volatile compounds present in green and roasted coffee beans have been extensively described, no study has yet linked varietal molecular differences to the greater abundance of specific substances and support the aroma specificity of specialty coffees. RESULTS: This study compared four Arabica genotypes including one, Geisha Especial, suggested to generate specialty coffee. Formal sensory evaluations of coffee beverages stressed the importance of coffee genotype in aroma perception and that Geisha Especial-made coffee stood out by having fine fruity, and floral, aromas and a more balanced acidity. Comparative SPME-GC-MS analyses of green and roasted bean volatile compounds indicated that those of Geisha Especial differed by having greater amounts of limonene and 3-methylbutanoic acid in agreement with the coffee cup aroma perception. A search for gene ontology differences of ripening beans transcriptomes of the four varieties revealed that they differed by metabolic processes linked to terpene biosynthesis due to the greater gene expression of prenyl-pyrophosphate biosynthetic genes and terpene synthases. Only one terpene synthase (CaTPS10-like) had an expression pattern that paralleled limonene loss during the final stage of berry ripening and limonene content in the studied four varieties beans. Its functional expression in tobacco leaves confirmed its functioning as a limonene synthase. CONCLUSIONS: Taken together, these data indicate that coffee variety genotypic specificities may influence ripe berry chemotype and final coffee aroma unicity. For the specialty coffee variety Geisha Especial, greater expression of terpene biosynthetic genes including CaTPS10-like, a limonene synthase, resulted in the greater abundance of limonene in green beans, roasted beans and a unique citrus note of the coffee drink.


Assuntos
Alquil e Aril Transferases , Coffea , Liases Intramoleculares , Odorantes , Coffea/genética , Limoneno , Terpenos , Sementes , Perfilação da Expressão Gênica
2.
Anal Chem ; 96(8): 3247-3252, 2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38349005

RESUMO

Proteomics is continually being applied to a wider range of applications, now including the analysis of archaeological samples and anatomical specimens, particularly collagen-containing tissues such as bones and teeth. Here, we present the application of a chemical digestion-based proteomics sample preparation protocol to the analysis of fresh, anatomical, and archaeological samples. We describe and discuss two protocols: one that uses hydroxylamine as an additional step of the proteomic workflow, applied to the insoluble fraction, and another that applies hydroxylamine directly on demineralized bones and teeth. We demonstrate the additional information that can be extracted using both protocols, including an increase in the sequence coverage and number of peptides detected in modern and archaeological samples and an increase in the number of proteins identified in archaeological samples. By targeting research related to collagens or extracellular matrix proteins, the use of this protocol will open new insights, considering both fresh and ancient mineralized samples.


Assuntos
Proteoma , Proteômica , Hidroxilamina , Proteômica/métodos , Osso e Ossos , Hidroxilaminas
3.
Diagnostics (Basel) ; 13(17)2023 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-37685346

RESUMO

In the fields of forensics, the identification of human remains is a recurrent problem. The estimated age at death is one of the copious criteria to be evaluated. In adult teeth, the height of the root dentin transparency is used to estimate age. However, in archaeological material, this phenomenon appears inconstant. The aim of this work was to observe the structural modifications of the sclerotic dentin in the teeth for different postmortem intervals. The study included two parts (retrospective and prospective study) with 21 human monoradicular teeth, from bodies donated to medical science with postmortem intervals (PMIs) of 0, 1, 2 and 5 years and archeological excavation. After inclusion based on resin, section and polishing, the samples were analyzed with a scanning electron microscope (SEM) JSM-7800F®, and the procedure was completed via a semiquantitative analysis of calcium and phosphorus using EDX microanalysis. The analysis showed the existence of tubular and chemical modifications of sclerotic dentin at different PMIs. Our SEM study allowed us to observe a difference in tubule aspects linked to an increased PMI: the loss of peritubular collar and the lumen obstruction of tubules with a hyperdense material. Microanalysis highlighted variations in phosphocalcic ratios among the different groups, especially in the pulp area and the canine. Our hypotheses that explain these differences are based on the postmortem modifications of the crystals of the mineral phase of sclerotic dentin under the influence of chemical and/or bacterial action.

4.
Chempluschem ; 88(11): e202300303, 2023 11.
Artigo em Inglês | MEDLINE | ID: mdl-37610058

RESUMO

A series of four binuclear complexes of general formula [(C^C)Au(Cl)(L^L)(Cl)Au(C^C)], where C^C is 4,4'-diterbutylbiphenyl and L^L is either a bridging diphosphine or 4,4'-bipyridine, are synthetized with 52 to 72 % yield and structurally characterized by X-ray diffraction. The use of the chelating 1,2-diphenylphosphinoethane ligand in a 1 : 2 (P^P):Au stoichiometry leads to the near quantitative formation of a gold double-complex salt of general formula [(C^C)Au(P^P)][(C^C^)AuCl2 ]. The compounds display long-lived yellow-green phosphorescence with λem in the range of 525 to 585 nm in the solid state with photoluminescence quantum yields (PLQY) up to 10 %. These AuIII complexes are tested for their antiproliferative activity against lung adenocarcinoma cells A549 and results show that compounds 2 and 5 are the most promising candidates. The digold salt 5 shows anticancer activity between 66 and 200 nM on the tested cancer cell lines, whereas derivative 2 displays concentration values required to reduce by 50 % the cell viability (IC50 ) between 7 and 11 µM. Reactivity studies of compound 5 reveal that the [(C^C)Au(P^P)]+ cation is stable in the presence of relevant biomolecules including glutathione suggesting a structural mechanism of action.


Assuntos
Antineoplásicos , Antineoplásicos/química , Compostos Organoáuricos/química , Linhagem Celular Tumoral , Compostos de Bifenilo
5.
Inorg Chem ; 62(33): 13304-13314, 2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37560906

RESUMO

In this work, we report on the synthesis of several organogold(III) complexes based on 4,4'-diterbutylbiphenyl (C^C) and 2,6-bis(4-terbutylphenyl)pyridine (C^N^C) ligands and bond with variously substituted pyridine ligands (pyrR). Altogether, 33 complexes have been prepared and studied with mass spectrometry using higher-energy collision dissociation (HCD) in an Orbitrap mass spectrometer. A complete methodology including the kinetic modeling of the dissociation process based on the Rice-Ramsperger-Kassel-Marcus (RRKM) statistical method is proposed to obtain critical energies E0 of the pyrR loss for all complexes. The capacity of these E0 values to describe the pyridine ligand effect is further explored, at the same time as more classical descriptors such as 1H pyridinic NMR shift variation upon coordination and Au-NpyrR bond length measured by X-ray diffraction. An extensive theoretical work, including density functional theory (DFT) and domain-based local pair natural orbital coupled-cluster theory (DLPNO-CCSD(T)) methods, is also carried out to provide bond-dissociation energies, which are compared to experimental results. Results show that dissociation energy outperforms other descriptors, in particular to describe ligand effects over a large electronic effect range as seen by confronting the results to the pyrR pKa values. Further insights into the Au-NpyrR bond are obtained through an energy decomposition analysis (EDA) study, which confirms the isolobal character of Au+ with H+. Finally, the correlation between the lability of the pyridine ligands toward the catalytic efficiency of the complexes could be demonstrated in an intramolecular hydroarylation reaction of alkyne. The results were rationalized considering both pre-catalyst activation and catalyst reactivity. This study establishes the possibility of correlating dissociation energy, which is a gas-phase descriptor, with condensed-phase parameters such as catalysis efficiency. It therefore holds great potential for inorganic and organometallic chemistry by opening a convenient and easy way to evaluate the electronic influence of a ligand toward a metallic center.

6.
Nat Nanotechnol ; 18(7): 741-746, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36879125

RESUMO

Spins in semiconductor quantum dots constitute a promising platform for scalable quantum information processing. Coupling them strongly to the photonic modes of superconducting microwave resonators would enable fast non-demolition readout and long-range, on-chip connectivity, well beyond nearest-neighbour quantum interactions. Here we demonstrate strong coupling between a microwave photon in a superconducting resonator and a hole spin in a silicon-based double quantum dot issued from a foundry-compatible metal-oxide-semiconductor fabrication process. By leveraging the strong spin-orbit interaction intrinsically present in the valence band of silicon, we achieve a spin-photon coupling rate as high as 330 MHz, largely exceeding the combined spin-photon decoherence rate. This result, together with the recently demonstrated long coherence of hole spins in silicon, opens a new realistic pathway to the development of circuit quantum electrodynamics with spins in semiconductor quantum dots.

7.
J Sci Food Agric ; 103(9): 4692-4703, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36905183

RESUMO

BACKGROUND: The effects of the environment and genotype in the coffee bean chemical composition were studied using nine trials covering an altitudinal gradient [600-1100 m above sea level (a.s.l.)] with three genotypes of Coffea arabica in the northwest mountainous region of Vietnam. The impacts of the climatic conditions on bean physical characteristics and chemical composition were assessed. RESULTS: We showed that the environment had a significant effect on the bean density and on all bean chemical compounds. The environment effect was stronger than the genotype and genotype-environment interaction effects for cafestol, kahweol, arachidic (C20:0), behenic acid (C22:0), 2,3-butanediol, 2-methyl-2-buten-1-ol, benzaldehyde, benzene ethanol, butyrolactone, decane, dodecane, ethanol, pentanoic acid, and phenylacetaldehyde bean content. A 2 °C increase in temperature had more influence on bean chemical compounds than a 100 mm increase in soil water content. Temperature was positively correlated with lipids and volatile compounds. With an innovative method using iterative moving averages, we showed that correlation of temperature, vapour pressure deficit (VPD) and rainfall with lipids and volatiles was higher between the 10th and 20th weeks after flowering highlighting this period as crucial for the synthesis of these chemicals. Genotype specific responses were evidenced and could be considered in future breeding programmes to maintain coffee beverage quality in the midst of climate change. CONCLUSION: This first study of the effect of the genotype-environment interactions on chemical compounds enhances our understanding of the sensitivity of coffee quality to genotype environment interactions during bean development. This work addresses the growing concern of the effect of climate change on speciality crops and more specifically coffee. © 2023 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.


Assuntos
Coffea , Interação Gene-Ambiente , Coffea/química , Melhoramento Vegetal , Sementes/química , Lipídeos/análise
8.
Inorg Chem ; 62(12): 4903-4921, 2023 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-36897338

RESUMO

A series of ten cationic complexes of the general formula [(C^C)Au(P^P)]X, where C^C = 4,4'-di-tert-butyl-1,1'-biphenyl, P^P is a diphosphine ligand, and X is a noncoordinating counteranion, have been synthesized and fully characterized by means of chemical and X-ray structural methods. All the complexes display a remarkable switch-on of the emission properties when going from a fluid solution to a solid state. In the latter, long-lived emission with lifetime τ = 1.8-83.0 µs and maximum in the green-yellow region is achieved with moderate to high photoluminescence quantum yield (PLQY). This emission is ascribed to an excited state with a mainly triplet ligand-centered (3LC) nature. This effect strongly indicates that rigidification of the environment helps to suppress nonradiative decay, which is mainly attributed to the large molecular distortion in the excited state, as supported by density functional theory (DFT) and time-dependent DFT (TD-DFT) computation. In addition, quenching intermolecular interactions of the emitter are avoided thanks to the steric hindrance of the substituents. Emissive properties are therefore restored efficiently. The influence of both diphosphine and anion has been investigated and rationalized as well. Using two complexes as examples and owing to their enhanced optical properties in the solid state, the first proof-of-concept of the use of gold(III) complexes as electroactive materials for the fabrication of light-emitting electrochemical cell (LEC) devices is herein demonstrated. The LECs achieve peak external quantum efficiency, current efficiency, and power efficiency up to ca. 1%, 2.6 cd A-1, and 1.1 lm W-1 for complex 1PF6 and 0.9%, 2.5 cd A-1, and 0.7 lm W-1 for complex 3, showing the potential use of these novel emitters as electroactive compounds in LEC devices.

9.
BMC Genomics ; 24(1): 41, 2023 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-36694132

RESUMO

BACKGROUND: Somatic embryogenesis (SE) is one of the most promising processes for large-scale dissemination of elite varieties. However, for many plant species, optimizing SE protocols still relies on a trial and error approach. We report the first global scale transcriptome profiling performed at all developmental stages of SE in coffee to unravel the mechanisms that regulate cell fate and totipotency. RESULTS: RNA-seq of 48 samples (12 developmental stages × 4 biological replicates) generated 90 million high quality reads per sample, approximately 74% of which were uniquely mapped to the Arabica genome. First, the statistical analysis of transcript data clearly grouped SE developmental stages into seven important phases (Leaf, Dedifferentiation, Primary callus, Embryogenic callus, Embryogenic cell clusters, Redifferentiation and Embryo) enabling the identification of six key developmental phase switches, which are strategic for the overall biological efficiency of embryo regeneration. Differential gene expression and functional analysis showed that genes encoding transcription factors, stress-related genes, metabolism-related genes and hormone signaling-related genes were significantly enriched. Second, the standard environmental drivers used to control SE, i.e. light, growth regulators and cell density, were clearly perceived at the molecular level at different developmental stages. Third, expression profiles of auxin-related genes, transcription factor-related genes and secondary metabolism-related genes were analyzed during SE. Gene co-expression networks were also inferred. Auxin-related genes were upregulated during dedifferentiation and redifferentiation while transcription factor-related genes were switched on from the embryogenic callus and onward. Secondary metabolism-related genes were switched off during dedifferentiation and switched back on at the onset of redifferentiation. Secondary metabolites and endogenous IAA content were tightly linked with their respective gene expression. Lastly, comparing Arabica embryogenic and non-embryogenic cell transcriptomes enabled the identification of biological processes involved in the acquisition of embryogenic capacity. CONCLUSIONS: The present analysis showed that transcript fingerprints are discriminating signatures of cell fate and are under the direct influence of environmental drivers. A total of 23 molecular candidates were successfully identified overall the 12 developmental stages and can be tested in many plant species to optimize SE protocols in a rational way.


Assuntos
Coffea , Perfilação da Expressão Gênica , Transcriptoma , Ácidos Indolacéticos/metabolismo , Regeneração , Fatores de Transcrição/metabolismo , Técnicas de Embriogênese Somática de Plantas , Regulação da Expressão Gênica de Plantas
10.
Org Lett ; 25(1): 256-260, 2023 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-36580358

RESUMO

Commercially available Fe(TTP)Cl catalyzes three-component dearomative formal cycloaddition reactions between pyridines, diazo compounds, and coumalates. Diversely substituted annelated seven-membered N-heterocycles could be generated in less than 10 min in one step at room temperature. The reaction is compatible to gram scale. The extension to benzimidazoles in place of pyridines has been successfully demonstrated. The mechanism of this reaction has been carefully examined by computational studies that corroborate the observed regioselectivities.

11.
J Sci Food Agric ; 103(7): 3602-3612, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36418192

RESUMO

BACKGROUND: Of the 130 known coffee (Coffea) species, very few have been properly evaluated for their beverage quality. The diversity of wild coffee species is considered critical to the long-term sustainability of the coffee sector, particularly under climate change. The challenge is finding coffee crops that satisfy agronomic criteria, now and under the altered climatic conditions of the future, as well as consumer requirements for flavour. We evaluated the sensory characteristics of three wild coffee species with four independent sensory panels, and the key environmental/agronomic requirements of these wild species based on a literature review. RESULTS: Coffea congensis and C. stenophylla have a lower unroasted seed weight compared to C. arabica and C. canephora, while C. brevipes has the largest. Sensory analysis showed that the main differences between species was for the fruitiness attribute. Coffea stenophylla was the fruitiest wild species, and was considered an Arabica-like coffee. The flavour profile range of C. stenophylla covers herb-like, vegetal, floral and fruit; C. brevipes resembles C. stenophylla in some respects. Opinions concerning C. congensis were contradictory and several judges considered the industry-standard coffee flavour wheel not suitable for the beverage produced from this species. CONCLUSION: The three wild species have the required sensory qualities for commercialization. According to published data, C. stenophylla has agronomic potential, especially in warmer climates than Arabica areas. Coffea brevipes and C. congensis have the potential to be easily crossed with C. canephora to form interspecific hybrids capable of adapting to different climatic and agronomic conditions. © 2022 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.


Assuntos
Coffea , Café , Frutas , Sementes , Agricultura
12.
Plants (Basel) ; 11(16)2022 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-36015436

RESUMO

Climate change (CC) is already impacting Arabica coffee cultivation in the intertropical zone. To deal with this situation, it is no longer possible to manage this crop using industrial agriculture techniques, which has been the main strategy implemented since the Green Revolution. Developing a more sustainable agriculture system that respects people and the environment is essential to guarantee future generations' access to natural resources. In the case of Arabica coffee, the solution has been found. Agroforestry is proposed as an ecosystem-based strategy to mitigate and adapt to CC. At least 60% of Arabica coffee is produced in agroforestry systems (AFSs), which are the most sustainable way to produce coffee. Nevertheless, AFS coffee cultivation is currently uncompetitive partly because all modern varieties, selected for full-sun intensive cropping systems, have low yields in shaded environments. Here we review the reasons why agroforestry is part of the solution to CC, and why no breeding work has been undertaken for this cropping system. Based on the literature data, for breeding purposes we also define for the first time one possible coffee ideotype required for AFS coffee cultivation. The four main traits are: (1) productivity based on F1 hybrid vigor, tree volume and flowering intensity under shade; (2) beverage quality by using wild Ethiopian accessions as female progenitors and selecting for this criterion using specific biochemical and molecular predictors; (3) plant health to ensure good tolerance to stress, especially biotic; and (4) low fertilization to promote sustainable production. For each of these traits, numerous criteria with threshold values to be achieved per trait were identified. Through this research, an ecosystem-based breeding strategy was defined to help create new F1 hybrid varieties within the next 10 years.

13.
G3 (Bethesda) ; 12(9)2022 08 25.
Artigo em Inglês | MEDLINE | ID: mdl-35792875

RESUMO

Genomic prediction has revolutionized crop breeding despite remaining issues of transferability of models to unseen environmental conditions and environments. Usage of endophenotypes rather than genomic markers leads to the possibility of building phenomic prediction models that can account, in part, for this challenge. Here, we compare and contrast genomic prediction and phenomic prediction models for 3 growth-related traits, namely, leaf count, tree height, and trunk diameter, from 2 coffee 3-way hybrid populations exposed to a series of treatment-inducing environmental conditions. The models are based on 7 different statistical methods built with genomic markers and ChlF data used as predictors. This comparative analysis demonstrates that the best-performing phenomic prediction models show higher predictability than the best genomic prediction models for the considered traits and environments in the vast majority of comparisons within 3-way hybrid populations. In addition, we show that phenomic prediction models are transferrable between conditions but to a lower extent between populations and we conclude that chlorophyll a fluorescence data can serve as alternative predictors in statistical models of coffee hybrid performance. Future directions will explore their combination with other endophenotypes to further improve the prediction of growth-related traits for crops.


Assuntos
Café , Fenômica , Clorofila A , Café/genética , Genoma de Planta , Genômica/métodos , Genótipo , Hibridização Genética , Modelos Genéticos , Fenótipo , Melhoramento Vegetal
14.
Phys Rev Lett ; 128(19): 197701, 2022 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-35622052

RESUMO

Josephson parametric amplifiers (JPAs) approaching quantum-limited noise performance have been instrumental in enabling high fidelity readout of superconducting qubits and, recently, semiconductor quantum dots (QDs). We propose that the quantum capacitance arising in electronic two-level systems (the dual of Josephson inductance) can provide an alternative dissipationless nonlinear element for parametric amplification. We experimentally demonstrate phase-sensitive parametric amplification using a QD-reservoir electron transition in a CMOS nanowire split-gate transistor embedded in a 1.8 GHz superconducting lumped-element microwave cavity, achieving parametric gains of -3 to +3 dB, limited by Sisyphus dissipation. Using a semiclassical model, we find an optimized design within current technological capabilities could achieve gains and bandwidths comparable to JPAs, while providing complementary specifications with respect to integration in semiconductor platforms or operation at higher magnetic fields.

15.
Open Res Eur ; 2: 61, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-37645280

RESUMO

Background: Worldwide coffee production, especially Arabica coffee, is threatened by climatic change, plants diseases and vulnerability of smallholders. Meanwhile, consumers' demand for socially and environmentally sustainable products is steadily increasing, driving the engagement of stakeholders in agro-ecological and social initiatives. Here we present a new organizational model, the "Coffee agroforestry business-driven cluster" (CaFC), which aims at preserving ecosystems while offering producers a fair income. Based on an original local micro value-chain dedicated to sustainable production of high-quality Arabica coffee under agroforestry systems, the CaFC model stands out by addressing the issues around plantation renovation, a crucial process that requires considerable investments from producers. Methods: Based on a pilot project in Nicaragua, we illustrate how the operational principles of CaFC can be applied in a real setting. Using data shared by key stakeholders involved in the project, we assess the profitability of the CaFC model by comparing different scenarios and applying sensitivity analysis. We then reflect on the reproducibility of the model in other contexts, building on lessons learned from ongoing implementations in Vietnam and Cameroon. Results: For producers renovating their plantations, the CaFC model consistently outperforms other scenarios, offering high quality premiums coupled with capacity building, access to highly productive varieties that perform well under agroforestry systems and adapted credit with favourable repayment schemes. Implementation in Vietnam and Cameroon show that the model can be successfully replicated with some adaptation to local contexts. These cases also highlight the importance of mutual interests, trust and communication in enabling collaboration between stakeholders. Conclusions: The CaFC model has great potential for positive environmental and economic impact and offers strong incentives for stakeholders involved in its resulting micro value-chain. The concept was initially developed in Nicaragua for coffee but could also be adapted in other countries or even to other commodities such as cocoa.

16.
Am J Biol Anthropol ; 179(2): 314-326, 2022 10.
Artigo em Inglês | MEDLINE | ID: mdl-36790742

RESUMO

It has been repeatedly acknowledged that age-at-death estimation based on dental cementum represents a partial and time-consuming method that hinders adoption of this histological approach. User-friendly micrograph analysis represents a growing request of cementochronology. This article evaluates the feasibility of using a module to accurately quantify cementum deposits and compares the module's performance to that of a human expert. On a dental collection (n = 200) of known-age individuals, precision and accuracy of estimates performed by a developed program (101 count/tooth; n = 20,200 counts) were compared to counts performed manually (5 counts/tooth; n = 975 counts). Reliability of the software and agreement between the two approaches were assessed by intraclass correlation coefficient and Bland Altman analysis. The automated module produced reliable and reproducible counts with a higher global precision than the human expert. Although the software is slightly more precise, it shows higher sensitivity to taphonomic damages and does not avoid the trajectory effect described for age-at-death estimation in adults. Likewise, for human counts, global accuracy is acceptable, but underestimations increase with age. The quantification of the agreement between the two approaches shows a minor bias, and 94% of individuals fall within the intervals of agreement. Automation gives an impression of objectivity even though the region of interest, profile position and parameters are defined manually. The automated system may represent a time-saving module that can allow an increase in sample size, which is particularly stimulating for population-based studies.


Assuntos
Determinação da Idade pelos Dentes , Adulto , Humanos , Reprodutibilidade dos Testes , Determinação da Idade pelos Dentes/métodos , Microscopia/métodos , Software
17.
Chemistry ; 27(63): 15773-15785, 2021 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-34436799

RESUMO

A library of eleven cationic gold(III) complexes of the general formula [(C C)Au(N N)]+ when C C is either biphenyl or 4,4'-ditertbutyldiphenyl and N N is a bipyridine, phenanthroline or dipyridylamine derivative have been synthesized and characterized. Contrasting effects on the viability of the triple negative breast cancer cells MDA-MB-231 was observed from a preliminary screening. The antiproliferative activity of the seven most active complexes were further assayed on a larger panel of human cancer cells as well as on non-cancerous cells for comparison. Two complexes stood out for being either highly active or highly selective. Eventually, reactivity studies with biologically meaningful amino acids, glutathione, higher order DNA structures and thioredoxin reductase (TrxR) revealed a markedly different behavior from that of the well-known coordinatively isomeric [(C N C)Au(NHC)]+ structure. This makes the [(C C)Au(N N)]+ complexes a new class of organogold compounds with an original mode of action.


Assuntos
Antineoplásicos , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Proliferação de Células , Ouro/farmacologia , Humanos , Compostos Organoáuricos/farmacologia , Tiorredoxina Dissulfeto Redutase
19.
ChemSusChem ; 14(8): 1821-1824, 2021 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-33651919

RESUMO

A general, sustainable dearomatization reaction for nitrogen-containing heterocycles was developed. Under solvent free conditions and without catalyst, the biorenewable methyl coumalate (MC) reacted as an efficient C3 partner to convert nine types of basic aromatic rings into their pyrido[1,2-a] fused derivatives in good to excellent yields. The fluorescence properties of some of the products were harnessed to conjugate fluorescent tags to bovine serum albumin (BSA) and immunoglobulin G.


Assuntos
Corantes Fluorescentes/química , Compostos Heterocíclicos/síntese química , Hidrocarbonetos Aromáticos/síntese química , Anisóis/química , Benzofuranos/química , Catálise , Reação de Cicloadição , Imunoglobulina G/química , Indóis/química , Estrutura Molecular , Imagem Óptica , Pironas/química , Pirróis/química , Soroalbumina Bovina/química , Solventes/química
20.
Tree Physiol ; 41(2): 302-316, 2021 02 02.
Artigo em Inglês | MEDLINE | ID: mdl-33080620

RESUMO

Photoperiod length induces in temperate plants major changes in growth rates, morphology and metabolism with, for example, modifications in the partitioning of photosynthates to avoid starvation at the end of long nights. However, this has never been studied for a tropical perennial species adapted to grow in a natural photoperiod close to 12 h/12 h all year long. We grew Coffea arabica L., an understorey perennial evergreen tropical species in its natural 12 h/12 h and in a short 8 h/16 h photoperiod, and we investigated its responses at the physiological, metabolic and transcriptomic levels. The expression pattern of rhythmic genes, including core clock genes, was affected by changes in photoperiod. Overall, we identified 2859 rhythmic genes, of which 89% were also rhythmic in Arabidopsis thaliana L. Under short-days, plant growth was reduced, and leaves were thinner with lower chlorophyll content. In addition, secondary metabolism was also affected with chlorogenic acid and epicatechin levels decreasing, and in agreement, the genes involved in lignin synthesis were overexpressed and those involved in the flavanol pathway were underexpressed. Our results show that the 8 h/16 h photoperiod induces drastic changes in morphology, metabolites and gene expression, and the responses for gene expression are similar to those observed in the temperate annual A. thaliana species. Short photoperiod induces drastic changes in gene expression, metabolites and leaf structure, some of these responses being similar to those observed in A. thaliana.


Assuntos
Coffea , Fotoperíodo , Coffea/genética , Regulação da Expressão Gênica de Plantas , Genes de Plantas/genética , Redes e Vias Metabólicas/genética
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