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1.
J Am Chem Soc ; 146(12): 8659-8667, 2024 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-38407928

RESUMO

The solid-state synthesis of single-crystalline organic polymers, having functional properties, remains an attractive and developing research area in polymer chemistry and materials science. However, light-triggered topochemical synthesis of crystalline polymers comprising an organoboron backbone has not yet been reported. Here, we describe an intriguing example of single-crystal-to-single-crystal (SCSC) rapid photosynthesis (occurs on a seconds-scale) of two structurally different linear organoboron polymers, driven by environmentally sustainable visible/sun light, obtained from the same monomer molecule. A newly designed Lewis acid-base type molecular B ← N organoboron adduct (consisting of an organoboron core and naphthylvinylpyridine ligands) crystallizes in two solid-state forms featuring the same chemical structure but different 3D structural topologies, namely, monomers 1 and 2. The solvate molecule-free crystals of 1 undergo topochemical photopolymerization via an unusual olefin-naphthyl ring [2 + 2] cyclization to yield the single crystalline [3]-ladderane polymer 1P growing along the B ← N linkages, accompanied by instantaneous and violent macroscopic mechanical motions or photosalient effects (such as bending-reshaping and jumping motions). In contrast, visible light-harvesting single crystals of 2 quantitatively polymerize to a B ← N bond-stabilized polymer 2P in a SCSC fashion owing to the rapid [2 + 2] cycloaddition reaction among olefin double bonds. Such olefin bonds in the crystals of 2 are suitably preorganized for photoreaction due to the presence of solvate molecules in the crystal packing. Single crystals of 2 also show photodynamic jumping motions - in response to visible light but in a relatively slower fashion than the crystals of 1. In addition to SCSC topochemical polymerization and dynamic motions, both monomer crystals and their single-crystalline polymers feature green emissive and short-lived room-temperature phosphorescence properties upon excitation with visible-light wavelength.

2.
J Am Chem Soc ; 146(19): 13113-13125, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38700843

RESUMO

Defect engineering in metal-organic frameworks (MOFs) has gained worldwide research traction, as it offers tools to tune the properties of MOFs. Herein, we report a novel 2-fold interpenetrated Bi-based MOF made of a tritopic flexible organic linker, followed by missing-linker defect engineering. This procedure creates a gradually augmented micro- and mesoporosity in the parent (originally nonporous) network. The resulting MOFs can tolerate a remarkable extent of linker vacancy (with absence of up to 60% of linkers per Bi node) created by altering the crystal-growth rate as a function of synthesis temperature and duration. Owing to the enhanced porosity and availability of the uncoordinated Lewis acidic Bi sites, the defect-engineered MOFs manifested improved surface areas, augmented CO2 and water vapor uptake, and catalytic activity. Parallel to this, the impact of defect engineering on the optoelectronic properties of these MOFs has also been studied, offering avenues for new applications.

3.
Chemistry ; 30(19): e202303072, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38308544

RESUMO

Using a straightforward sequence of diphosphonylation and a Pd-catalysed concerted-metalation-deprotonation (CMD), a synthetic strategy towards polyaromatic phosphorus containing heterocycles was developed. Herein, we report the synthesis and characterization of new azaphosphaphenalenes, using easily accessible palladium catalysts and starting materials. The key tetrahydroquinoline intermediates of the reaction were synthesised via a fast and effective procedure and could be isolated as such, or further reacted towards the target polyaromatic structures. The obtained products showed interesting luminescent properties and their emission, excitation and quantum yields were evaluated.

4.
Mar Drugs ; 21(12)2023 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-38132946

RESUMO

Alginate-based materials have gained significant attention in the medical industry due to their biochemical properties. In this article, we aimed to synthesize Cotton-Alginate-Copper Composite Materials (COT-Alg(-)Cu(2+)). The main purpose of this study was to assess the biochemical properties of new composites in the area of blood plasma coagulation processes, including activated partial thromboplastin time (aPTT), prothrombin time (PT), and thrombin time (TT). This study also involved in vitro antimicrobial activity evaluation of materials against representative colonies of Gram-positive and Gram-negative bacteria and antifungal susceptibility tests. The materials were prepared by immersing cotton fibers in an aqueous solution of sodium alginate, followed by ionic cross-linking of alginate chains within the fibers with Cu(II) ions to yield antimicrobial activity. The results showed that the obtained cotton-alginate-copper composites were promising materials to be used in biomedical applications, e.g., wound dressing.


Assuntos
Alginatos , Cobre , Cobre/química , Alginatos/química , Antibacterianos/farmacologia , Antibacterianos/química , Bactérias Gram-Negativas , Bactérias Gram-Positivas , Coagulação Sanguínea , Tempo de Protrombina , Tempo de Tromboplastina Parcial , Íons/farmacologia
5.
Chem Soc Rev ; 51(16): 6893-6908, 2022 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-35912511

RESUMO

Recent advances reveal that upconversion (UC) luminescent materials are highly important not just from a scientific, but also from a future application standpoint. Although significant progress has been made in this field in recent decades, still their versatile applications are hindered by the low upconversion luminescence intensity and low tuneability, which has hampered further implementation in real life applications. We find it highly beneficial to compile a summary of recent relevant literature and propose ways to enhance upconversion efficiency in lanthanide nanomaterials. One very promising way to tackle this problem is through implementing transition metal ion co-dopants into the materials, which is the focus of this tutorial review. In this review, the recent studies related to the tailored design of UC materials with transition metal ion co-dopants have been summarized, and the desirable functionality of transition metal ions in the host matrixes has been discussed. Apart from improving the upconversion efficiency, the implementation of transition metal-co-dopants into lanthanide upconversion materials has recently sparked interest in applications such as in vivo imaging, drug delivery or nanothermometers.


Assuntos
Elementos da Série dos Lantanídeos , Nanopartículas , Elementos de Transição , Íons , Luz , Luminescência
6.
Angew Chem Int Ed Engl ; 62(28): e202304722, 2023 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-37171876

RESUMO

In the quest for essential energy solutions towards an ecological friendly future, the transformation of visible light/solar energy into mechanical motions in metal-free luminescent crystals offers a sustainable choice of smart materials for lightweight actuating, and all-organic electronic devices. Such green energy-triggered photodynamic motions with room temperature phosphorescence (RTP) emission in molecular crystals have not been reported yet. Here, we demonstrate three new stoichiometrically different Lewis acid-base molecular organoboron crystals (PS1, PS2, and PS3), which exhibit rapid photosalient effects (ballistic splitting, moving, and jumping) under both ultraviolet (UV) and visible light associated with quantitative single-crystal-to-single-crystal (SCSC) [2+2] cycloaddition of preorganized olefins. Furthermore, these systems respond to sunlight and mobile (white) flashlight with a complete SCSC transformation in a relatively slow fashion. Remarkably, all PS1, PS2, and PS3 crystals display visible light-promoted dynamic green RTP as their emission peaks promptly blue-shift, due to instantaneous photomechanical effects. Time-dependent structural mapping of intermediate photoproducts during fast SCSC [2+2] photoreaction, by X-ray photodiffraction, reveals a rationale for the origin of these photodynamic motions associated with rapid topochemical transformations. The reported light-driven behavior (mechanical motions, dynamic phosphorescence, and topochemical reactivity), is considered advantageous for the strategic design of stimuli-responsive multi-functional crystalline materials.

7.
J Am Chem Soc ; 144(48): 22051-22058, 2022 12 07.
Artigo em Inglês | MEDLINE | ID: mdl-36417296

RESUMO

Photoluminescent molecular crystals integrated with the ability to transform light energy into macroscopic mechanical motions are a promising choice of materials for both actuating and photonic devices. However, such dynamic photomechanical effects, based on molecular organoboron compounds as well as phosphorescent crystalline materials, are not yet known. Here we present an intriguing example of photomechanical molecular single crystals of a newly synthesized organoboron containing Lewis acid-base molecular adduct (BN1, substituted triphenylboroxine and 1,2-di(4-pyridyl)ethylene) having a capsule shape molecular geometry. The single crystals of BN1 under UV light exhibit controllable rapid bending-shape recovery, delamination, violent splitting-jumping, and expanding features. The detailed structural investigation by single-crystal X-ray diffraction and 1H NMR spectroscopy reveals that the photosalient behavior of the BN1 single crystals is driven by a crystal-to-crystal [2 + 2] cycloaddition reaction, supported by four donor-acceptor type B←N bonds. The instant photomechanical reaction in the BN1 crystals occurs under UV on account of sudden release of stress associated with the strained molecular geometry, significant solid-state molecular movements (supramolecular change), and cleavage of half intermolecular B←N linkages to result in a complete photodimerized single-crystalline product via the existence of two other intermediate photoproducts. In addition, the BN1 crystals display short-lived room temperature phosphorescence, and the photodynamic events are accompanied by the enhancement of their phosphorescence intensity to yield the photoproduct. Interestingly, the molecular crystals of the final photoproduct polymerize at ambient conditions when recrystallized from the solution forming a 2D supramolecular crystalline polymer stabilized by the retention of all B←N coordination modes.


Assuntos
Reação de Cicloadição
8.
J Food Sci Technol ; 59(5): 1756-1768, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35531388

RESUMO

The aim of the study was to develop and compare the predictive models of lipid oxidation in minced raw pork meat enriched with selected plant extracts (allspice, basil, bay leaf, black seed, cardamom, caraway, cloves, garlic, nutmeg, onion, oregano, rosemary and thyme) by investigation TBARS values changes during storage at different temperatures. Meat samples with extract addition were stored under various temperatures (4, 8, 12, 16, and 20°C). TBARS values changes in samples stored at 12°C were used as external validation dataset. Lipid oxidation was evaluated by the TBARS content. Lipid oxidation increased with storage time and temperature. The dependence of lipid oxidation on temperature was adequately modelled by the Arrhenius and log-logistic equation with high R2 coefficients (0.98-0.99). Kinetic models and artificial neural networks (ANNs) were used to build the predictive models. The obtained result demonstrates that both kinetic Arrhenius (R 2 = 0.83) and log-logistic (R 2 = 0.84) models as well as ANN (R 2 = 0.99) model can predict TBARS changes in raw ground pork meat during storage.

9.
Phys Rev Lett ; 127(26): 263001, 2021 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-35029494

RESUMO

The leading quantum electrodynamic corrections to the nuclear magnetic shielding in one- and two-electron atomic systems are obtained in a complete form, and the shielding constants of ^{1}H, ^{3}He^{+}, and ^{3}He are calculated to be 17.735 436(3)×10^{-6}, 35.507 434(9)×10^{-6}, and 59.967 029(23)×10^{-6}, respectively. These results are orders of magnitude more accurate than previous ones, and, with the ongoing measurement of the nuclear magnetic moment of ^{3}He^{+} and planned ^{3}He^{2+}, they open the window for high-precision absolute magnetometry using ^{3}He NMR probes. The presented theoretical approach is applicable to all other light atomic and molecular systems, which facilitates the improved determination of magnetic moments of any light nuclei.

10.
Chemistry ; 27(25): 7214-7230, 2021 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-33539627

RESUMO

The market share of noncontact temperature sensors is expending due to fast technological and medical evolutions. In the wide variety of noncontact sensors, lanthanide-based temperature sensors stand out. They benefit from high photostability, relatively long decay times and high quantum yields. To circumvent their low molar light absorption, the incorporation of a light-harvesting antenna is required. This Review provides an overview of the nitrogen-rich antennae in lanthanide-based temperature sensors, emitting in the visible light spectrum, and discusses their temperature sensor ability. The N-rich ligands are incorporated in many different platforms. The investigation of different antennae is required to develop temperature sensors with diverse optical properties and to create a diverse offer for the multiple application fields. Molecular probes, consisting of small molecules, are first discussed. Furthermore, the thermometer properties of ratiometric temperature sensors, based on di- and polynuclear complexes, metal-organic frameworks, periodic mesoporous organosilicas and porous organic polymers, are summarized. The antenna mainly determines the application potential of the ratiometric thermometer. It can be observed that molecular probes are operational in the broad physiological range, metal-organic frameworks are generally very useful in the cryogenic region, periodic mesoporous organosilica show temperature dependency in the physiological range, and porous organic polymers are operative in the cryogenic-to-medium temperature range.

11.
Chemistry ; 27(21): 6479-6488, 2021 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-33476058

RESUMO

In recent years, luminescent materials doped with Ln3+ ions have attracted much attention for their application as optical thermometers based on both downshifting and upconversion processes. This study presents research done on the development of highly sensitive optical thermometers in the physiological temperature range based on poly(methyl methacrylate) (PMMA) films doped with two series of visible Ln3+ complexes (Ln3+ =Tb3+ , Eu3+ , and Sm3+ ) and SiO2 nanoparticles (NPs) coated with these PMMA films. The best performing PMMA film doped with Tb3+ and Eu3+ complexes was the PMMA[TbEuL1 tppo]1 film (L1 =4,4,4-trifluoro-1-phenyl-1,3-butadionate; tppo=triphenylphosphine oxide), which showed good temperature sensing of Sr =4.21 % K-1 at 313 K, whereas for the PMMA films doped with Tb3+ and Sm3+ complexes the best performing was the PMMA[TbSmL2 tppo]3 film (L2 =4,4,4-trifluoro-1-(4-chlorophenyl)-1,3-butadionate), with Sr =3.64 % K-1 at 313 K. Additionally, SiO2 NPs coated with the best performing films from each of the series of PMMA films (Tb-Eu and Tb-Sm) and their temperature-sensing properties were studied in water, showing excellent performance in the physiological temperature range (PMMA[TbEuL1 tppo]1@SiO2 : Sr =3.84 % °C at 20 °C; PMMA[TbSmL2 tppo]3@SiO2 : Sr =3.27 % °C at 20 °C) and the toxicity of these nanoparticles on human cells was studied, showing that they were nontoxic.


Assuntos
Nanopartículas , Polimetil Metacrilato , Humanos , Dióxido de Silício , Temperatura , Termômetros
12.
Mol Cell Proteomics ; 18(10): 1916-1938, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31311849

RESUMO

The precise regulation of synaptic integrity is critical for neuronal network connectivity and proper brain function. Essential aspects of the activity and localization of synaptic proteins are regulated by posttranslational modifications. S-palmitoylation is a reversible covalent modification of the cysteine with palmitate. It modulates affinity of the protein for cell membranes and membranous compartments. Intracellular palmitoylation dynamics are regulated by crosstalk with other posttranslational modifications, such as S-nitrosylation. S-nitrosylation is a covalent modification of cysteine thiol by nitric oxide and can modulate protein functions. Therefore, simultaneous identification of endogenous site-specific proteomes of both cysteine modifications under certain biological conditions offers new insights into the regulation of functional pathways. Still unclear, however, are the ways in which this crosstalk is affected in brain pathology, such as stress-related disorders. Using a newly developed mass spectrometry-based approach Palmitoylation And Nitrosylation Interplay Monitoring (PANIMoni), we analyzed the endogenous S-palmitoylation and S-nitrosylation of postsynaptic density proteins at the level of specific single cysteine in a mouse model of chronic stress. Among a total of 813 S-PALM and 620 S-NO cysteine sites that were characterized on 465 and 360 proteins, respectively, we sought to identify those that were differentially affected by stress. Our data show involvement of S-palmitoylation and S-nitrosylation crosstalk in the regulation of 122 proteins including receptors, scaffolding proteins, regulatory proteins and cytoskeletal components. Our results suggest that atypical crosstalk between the S-palmitoylation and S-nitrosylation interplay of proteins involved in synaptic transmission, protein localization and regulation of synaptic plasticity might be one of the main events associated with chronic stress disorder, leading to destabilization in synaptic networks.


Assuntos
Neurônios/citologia , Óxido Nítrico/metabolismo , Proteômica/métodos , Estresse Fisiológico , Sinapses/metabolismo , Animais , Células Cultivadas , Cromatografia Líquida , Cisteína/metabolismo , Regulação da Expressão Gênica , Lipoilação , Masculino , Camundongos , Plasticidade Neuronal , Neurônios/metabolismo , Processamento de Proteína Pós-Traducional , Transporte Proteico , Espectrometria de Massas em Tandem
13.
Int J Mol Sci ; 22(18)2021 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-34576064

RESUMO

S-palmitoylation is a reversible covalent post-translational modification of cysteine thiol side chain by palmitic acid. S-palmitoylation plays a critical role in a variety of biological processes and is engaged in several human diseases. Therefore, identifying specific sites of this modification is crucial for understanding their functional consequences in physiology and pathology. We present a random forest (RF) classifier-based consensus strategy (RFCM-PALM) for predicting the palmitoylated cysteine sites on synaptic proteins from male/female mouse data. To design the prediction model, we have introduced a heuristic strategy for selection of the optimum set of physicochemical features from the AAIndex dataset using (a) K-Best (KB) features, (b) genetic algorithm (GA), and (c) a union (UN) of KB and GA based features. Furthermore, decisions from best-trained models of the KB, GA, and UN-based classifiers are combined by designing a three-star quality consensus strategy to further refine and enhance the scores of the individual models. The experiment is carried out on three categorized synaptic protein datasets of a male mouse, female mouse, and combined (male + female), whereas in each group, weighted data is used as training, and knock-out is used as the hold-out set for performance evaluation and comparison. RFCM-PALM shows ~80% area under curve (AUC) score in all three categories of datasets and achieve 10% average accuracy (male-15%, female-15%, and combined-7%) improvements on the hold-out set compared to the state-of-the-art approaches. To summarize, our method with efficient feature selection and novel consensus strategy shows significant performance gains in the prediction of S-palmitoylation sites in mouse datasets.


Assuntos
Algoritmos , Simulação por Computador , Lipoilação , Proteínas do Tecido Nervoso/metabolismo , Sinapses/metabolismo , Animais , Bases de Dados de Proteínas , Feminino , Masculino , Camundongos
14.
Int J Mol Sci ; 22(12)2021 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-34200797

RESUMO

Although sex differences in the brain are prevalent, the knowledge about mechanisms underlying sex-related effects on normal and pathological brain functioning is rather poor. It is known that female and male brains differ in size and connectivity. Moreover, those differences are related to neuronal morphology, synaptic plasticity, and molecular signaling pathways. Among different processes assuring proper synapse functions are posttranslational modifications, and among them, S-palmitoylation (S-PALM) emerges as a crucial mechanism regulating synaptic integrity. Protein S-PALM is governed by a family of palmitoyl acyltransferases, also known as DHHC proteins. Here we focused on the sex-related functional importance of DHHC7 acyltransferase because of its S-PALM action over different synaptic proteins as well as sex steroid receptors. Using the mass spectrometry-based PANIMoni method, we identified sex-dependent differences in the S-PALM of synaptic proteins potentially involved in the regulation of membrane excitability and synaptic transmission as well as in the signaling of proteins involved in the structural plasticity of dendritic spines. To determine a mechanistic source for obtained sex-dependent changes in protein S-PALM, we analyzed synaptoneurosomes isolated from DHHC7-/- (DHHC7KO) female and male mice. Our data showed sex-dependent action of DHHC7 acyltransferase. Furthermore, we revealed that different S-PALM proteins control the same biological processes in male and female synapses.


Assuntos
Aciltransferases/fisiologia , Lipoilação , Plasticidade Neuronal , Neurônios/fisiologia , Processamento de Proteína Pós-Traducional , Sinapses/fisiologia , Transmissão Sináptica , Animais , Feminino , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Knockout , Neurônios/citologia , Fatores Sexuais
15.
Molecules ; 26(16)2021 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-34443539

RESUMO

During the shelf-life, meat undergoes a number of processes that negatively affect the quality of the product, including fatty acid composition. The application of various plant extracts in meat could affect the changes of fatty acids during storage. Thus, the aim of this study was to investigate the effect of various spice and herb extracts on fatty acid composition in raw pork, beef, and chicken meat when stored at 4 °C for 13 days. Based on multivariate statistical analysis, two datasets were extracted from each type of meat. One dataset included samples with allspice, bay leaf, black seed, cardamom, caraway, clove, and nutmeg with the high share of total MUFA (monounsaturated fatty acids) in chicken and pork meat and high MUFA and PUFA (polyunsaturated fatty acids) contribution in beef meat after storage. The second dataset included basil, garlic, onion, oregano, rosemary, and thyme with high PUFA share in chicken and pork meat and high SFA (saturated fatty acids) contribution in beef meat. From the regression analysis, a significant effect of time on fatty acid composition in meat was reported. Generally, the rates of fatty acid changes were dependent on the plant extract incorporated into the meat. The most visible effect of plant extracts was obtained in chicken meat. In chicken meat with plant extracts, the rates of SFA and PUFA changes with time were slower compared to the control sample. In summary, the fatty acid composition of intramuscular fat varied during storage, and the addition of plant extracts significantly affected the rate of these changes, which was dependent on the meat matrix.


Assuntos
Ácidos Graxos/análise , Extratos Vegetais/farmacologia , Carne de Porco/análise , Preservação Biológica , Carne Vermelha/análise , Refrigeração , Animais , Galinhas , Análise de Componente Principal , Análise de Regressão
16.
Molecules ; 26(7)2021 Mar 31.
Artigo em Inglês | MEDLINE | ID: mdl-33807192

RESUMO

The aim of this study was to describe the thermal properties of selected cultivars of flaxseed oil by the use of the differential scanning calorimetry (DSC) technique. The crystallization and melting profiles were analyzed depending on different scanning rates (1, 2, 5 °C/min) as well as oxidative induction time (OIT) isothermally at 120 °C and 140 °C, and oxidation onset temperatures (Ton) at 2 and 5 °C/min were measured. The crystallization was manifested as a single peak, differing for a cooling rate of 1 and 2 °C/min. The melting curves were more complex with differences among the cultivars for a heating rate of 1 and 2 °C/min, while for 5 °C/min, the profiles did not differ, which could be utilized in analytics for profiling in order to assess the authenticity of the flaxseed oil. Moreover, it was observed that flaxseed oil was highly susceptible to thermal oxidation, and its stability decreased with increasing temperature and decreasing heating rate. Significant negative linear correlations were found between unsaturated fatty acid content (C18:2, C18:3 n-3) and DSC parameters (OIT, Ton). Principal component analysis (PCA) also established a strong correlation between total oxidation value (TOTOX), peroxide value (PV) and all DSC parameters of thermo-oxidative stability.


Assuntos
Cristalização , Congelamento , Óleo de Semente do Linho/química , Ácidos Graxos Insaturados/análise , Calefação , Oxirredução
17.
Angew Chem Int Ed Engl ; 60(7): 3727-3736, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-33170988

RESUMO

Covalent Organic Frameworks (COFs), an emerging class of crystalline porous materials, are a new type of support for grafting lanthanide ions (Ln3+ ), which can be employed as ratiometric luminescent thermometers. In this work we have shown that COFs co-grafted with lanthanide ions (Eu3+ , Tb3+ ) and Cu2+ (or potentially other d-metals) can synchronously be employed both as a nanothermometer and catalyst during a chemical reaction. The performance of the thermometer could be tuned by changing the grafted d-metal and solvent environment. As a proof of principle, the Glaser coupling reaction was investigated. We show that temperature can be precisely measured during the course of the catalytic reaction using luminescence thermometry. This concept could be potentially easily extended to other catalytic reactions by grafting other d-metal ions on the Ln@COF platform.

18.
Plant J ; 98(1): 165-180, 2019 04.
Artigo em Inglês | MEDLINE | ID: mdl-30552776

RESUMO

Strigolactones (SLs) are a family of terpenoid allelochemicals that were recognized as plant hormones only a decade ago. They influence a myriad of both above- and below-ground developmental processes, and are an important survival strategy for plants in nutrient-deprived soils. A rapidly emerging approach to gain knowledge on hormone signaling is the use of traceable analogs. A unique class of labeled SL analogs was constructed, in which the original tricyclic lactone moiety of natural SLs is replaced by a fluorescent cyanoisoindole ring system. Biological evaluation as parasitic seed germination stimulant and hypocotyl elongation repressor proved the potency of the cyanoisoindole strigolactone analogs (CISAs) to be comparable to the commonly accepted standard GR24. Additionally, via a SMXL6 protein degradation assay, we provided molecular evidence that the compounds elicit SL-like responses through the natural signaling cascade. All CISAs were shown to exhibit fluorescent properties, and the high quantum yield and Stokes shift of the pyrroloindole derivative CISA-7 also enabled in vivo visualization in plants. In contrast to the previously reported fluorescent analogs, CISA-7 displays a large similarity in shape and structure with natural SLs, which renders the analog a promising tracer to investigate the spatiotemporal distribution of SLs in plants and fungi.


Assuntos
Proteínas de Arabidopsis/metabolismo , Arabidopsis/genética , Lactonas/química , Proteólise , Transdução de Sinais , Arabidopsis/fisiologia , Proteínas de Arabidopsis/genética , Corantes Fluorescentes , Germinação , Hipocótilo/genética , Hipocótilo/fisiologia , Reguladores de Crescimento de Plantas/metabolismo , Sementes/genética , Sementes/fisiologia
19.
Am J Hum Genet ; 100(2): 297-315, 2017 02 02.
Artigo em Inglês | MEDLINE | ID: mdl-28132687

RESUMO

Homozygous SMN1 loss causes spinal muscular atrophy (SMA), the most common lethal genetic childhood motor neuron disease. SMN1 encodes SMN, a ubiquitous housekeeping protein, which makes the primarily motor neuron-specific phenotype rather unexpected. SMA-affected individuals harbor low SMN expression from one to six SMN2 copies, which is insufficient to functionally compensate for SMN1 loss. However, rarely individuals with homozygous absence of SMN1 and only three to four SMN2 copies are fully asymptomatic, suggesting protection through genetic modifier(s). Previously, we identified plastin 3 (PLS3) overexpression as an SMA protective modifier in humans and showed that SMN deficit impairs endocytosis, which is rescued by elevated PLS3 levels. Here, we identify reduction of the neuronal calcium sensor Neurocalcin delta (NCALD) as a protective SMA modifier in five asymptomatic SMN1-deleted individuals carrying only four SMN2 copies. We demonstrate that NCALD is a Ca2+-dependent negative regulator of endocytosis, as NCALD knockdown improves endocytosis in SMA models and ameliorates pharmacologically induced endocytosis defects in zebrafish. Importantly, NCALD knockdown effectively ameliorates SMA-associated pathological defects across species, including worm, zebrafish, and mouse. In conclusion, our study identifies a previously unknown protective SMA modifier in humans, demonstrates modifier impact in three different SMA animal models, and suggests a potential combinatorial therapeutic strategy to efficiently treat SMA. Since both protective modifiers restore endocytosis, our results confirm that endocytosis is a major cellular mechanism perturbed in SMA and emphasize the power of protective modifiers for understanding disease mechanism and developing therapies.


Assuntos
Endocitose/genética , Atrofia Muscular Espinal/genética , Neurocalcina/metabolismo , Animais , Caenorhabditis elegans/genética , Linhagem Celular , Clonagem Molecular , Modelos Animais de Doenças , Feminino , Regulação da Expressão Gênica , Loci Gênicos , Estudo de Associação Genômica Ampla , Homozigoto , Humanos , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Neurônios Motores/patologia , Atrofia Muscular Espinal/terapia , Neurocalcina/genética , Células PC12 , Linhagem , Ratos , Proteína 1 de Sobrevivência do Neurônio Motor/genética , Proteína 1 de Sobrevivência do Neurônio Motor/metabolismo , Proteína 2 de Sobrevivência do Neurônio Motor/genética , Proteína 2 de Sobrevivência do Neurônio Motor/metabolismo , Transcriptoma , Peixe-Zebra/genética
20.
Chemistry ; 26(67): 15596-15604, 2020 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-32519784

RESUMO

The challenge of measuring fast moving or small scale samples is based on the absence of contact between sample and sensor. Grafting lanthanides onto hybrid materials arises as one of the most promising accurate techniques to obtain noninvasive thermometers. In this work, a novel bipyridine based porous organic polymer (bpyDAT POP) was investigated as temperature sensor after grafting with Eu(acac)3 and Tb(acac)3 complexes. The bpyDAT POP successfully showed temperature-dependent behavior in the 10-310 K range, proving the potential of amorphous, porous organic frameworks. We observed unique temperature dependent behavior. More intriguingly, instead of the standard observed change in emission as a result of a change in temperature for both Eu3+ and Tb3+ , the emission spectrum of Tb3+ remained constant. This work provides framework- and energy-based explanations for the observed phenomenon. The conjugation in the bpyDAT POP framework is interrupted, creating energetically isolated Tb3+ environments. Energy transfer from Tb3+ to Eu3+ is therefore absent, nor energy back transfer from Tb3+ to bpyDAT POP ligand (i.e. no thermal quenching) is detected.

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