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1.
Front Psychol ; 15: 1402885, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-39100558

RESUMO

Introduction: Exposure to natural environments, such as parks, forests, and green areas, is often linked to a decrease in stress, anxiety and depression, while contributing to improved emotional wellbeing. These observations are supported by well-established theories, such as the Stress Reduction Theory and Attention Restoration Theory, which highlight the psychological benefits of interacting with nature. However, the relationship between exposure to nature and emotions, and in particular, with emotional regulation, is an evolving aspect of research with no clear conclusions. Emotional regulation can be deliberate in nature, where individuals voluntarily participate in modifying various aspects of their emotions, such as their type, intensity, quality or duration. Alternatively, it may be automatic, originating from sensory perception and acting without full awareness, but significantly influencing emotional experiences. In this context, the environmental self-regulation hypothesis, suggests that people consciously or unconsciously use their physical environment to regulate their emotions. Method: To analyze the evidence of the relationship between contact with nature and emotional regulation, we conducted this review. Using the PRISMA statement as a reference, we conducted keyword searches in five databases in the period between 2013 and 2023. The databases selected were Scopus, Web of Science (WoS), PubMed, PsycINFO and ScienceDirect. Results: In addition, a manual search was carried out of journals in the research field. Initially, from which gray literature, reviews and duplicates were removed in a first step. The resulting articles were then filtered using their titles and abstracts. Subsequently, the abstracts of the 25 selected articles were reviewed and discussed by researchers to reach a final decision based on consensus about the adequacy of each paper. Finally, nine articles were included in the systematic review. Discussion: In general terms, this review suggests that research on the relationship between contact with nature and emotional regulation provides valuable insights into how natural environments can contribute to the emotional wellbeing and physical and mental health of the population.

2.
J Am Soc Mass Spectrom ; 35(5): 972-981, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38551491

RESUMO

The identification and quantitation of plasmalogen glycerophospholipids is challenging due to their isobaric overlap with plasmanyl ether-linked glycerophospholipids, susceptibility to acid degradation, and their typically low abundance in biological samples. Trimethylation enhancement using diazomethane (TrEnDi) can be used to significantly enhance the signal of glycerophospholipids through the creation of quaternary ammonium groups producing fixed positive charges using 13C-diazomethane in complex lipid extracts. Although TrEnDi requires a strong acid for complete methylation, we report an optimized protocol using 10 mM HBF4 with the subsequent addition of a buffer solution that prevents acidic hydrolysis of plasmalogen species and enables the benefits of TrEnDi to be realized for this class of lipids. These optimized conditions were applied to aliquots of bovine liver extract (BLE) to achieve permethylation of plasmalogen lipids within a complex mixture. Treating aliquots of unmodified and TrEnDi-derivatized BLE samples with 80% formic acid and comparing their liquid chromatography mass spectrometry (LCMS) results to analogous samples not treated with formic acid, enabled the identification of 29 plasmalogen species. On average, methylated plasmalogen species from BLE demonstrated 2.81-fold and 28.1-fold sensitivity gains over unmodified counterparts for phosphatidylcholine and phosphatidylethanolamine plasmalogen species, respectively. Furthermore, the compatibility of employing 13C-TrEnDi and a previously reported iodoacetalization strategy was demonstrated to effectively identify plasmenyl-ether lipids in complex biological extracts at greater levels of sensitivity. Overall, we detail an optimized 13C-TrEnDi derivatization strategy that enables the analysis of plasmalogen glycerophospholipids with no undesired cleavage of radyl groups, boosting their sensitivity in LCMS and LCMS/MS analyses.


Assuntos
Isótopos de Carbono , Diazometano , Glicerofosfolipídeos , Fígado , Plasmalogênios , Animais , Bovinos , Plasmalogênios/química , Plasmalogênios/análise , Isótopos de Carbono/análise , Diazometano/química , Fígado/química , Glicerofosfolipídeos/química , Glicerofosfolipídeos/análise , Metilação , Cromatografia Líquida/métodos , Espectrometria de Massas em Tandem/métodos
3.
J Am Soc Mass Spectrom ; 35(1): 140-150, 2024 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-38127770

RESUMO

Over the past century, agriculture practices have transitioned from manual cultivation to the use of an array of chemical herbicides for weed control including phosphinothricin, or glufosinate (GLUF). Consequently, the potential for long-term residual GLUF exposure in the food chain has increased, highlighting the need for improved analytical strategies for its detection, as well as the detection of its main breakdown product 3-(methylphosphinico)propionic acid (MPPA). Chemical derivatization strategies have been developed to improve the detection of GLUF and MPPA via liquid chromatography tandem mass spectrometry analyses. Herein, we employ trimethylation enhancement using diazomethane (TrEnDi) for the first time as a means to confer analytical advantages via quantitatively derivatizing these analytes into permethylated GLUF ([GLUFTr]+) and MPPA ([MPPATr+H]+). Comparing [GLUFTr]+ and [MPPATr+H]+ to underivatized counterparts, TrEnDi yields 2.8-fold and 1.7-fold improvements in reversed-phase chromatographic retention, respectively, while MS-based sensitivity is enhanced 4.1-fold and 11.0-fold, respectively. Successful analyte derivatization (with >99% yields) was further demonstrated on a commercial herbicide solution imparting consistent analytical enhancements. To investigate the benefits of TrEnDi in a bona fide agricultural scenario, simple aqueous extractions from distinct parts of field-grown canola plants were performed to quantify GLUF and MPPA before and after TrEnDi derivatization. In their underivatized forms, GLUF and MPPA were undetectable in all field samples, whereas [GLUFTr]+ and [MPPATr+H]+ were readily quantifiable using the same analysis conditions. Our results demonstrate that TrEnDi continues to be a useful tool to enhance the analytical characteristics of organic molecules that are traditionally difficult to detect.


Assuntos
Diazometano , Herbicidas , Diazometano/química , Herbicidas/análise , Aminobutiratos/análise
4.
J Am Soc Mass Spectrom ; 34(12): 2722-2730, 2023 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-37929927

RESUMO

13C-Trimethylation enhancement using diazomethane (13C-TrEnDi) is a chemical derivatization technique that uses 13C-labeled diazomethane to increase mass spectrometry (MS) signal intensities for phosphatidylcholine (PC) and phosphatidylethanolamine (PE) lipid classes, both of which are of major interest in biochemistry. In silico mass spectrometry databases have become mainstays in lipidomics experiments; however, 13C-TrEnDi-modified PC and PE species have altered m/z and fragmentation patterns from their native counterparts. To build a database of 13C-TrEnDi-modified PC and PE species, a lipid extract from nutritional yeast was derivatized and fragmentation spectra of modified PC and PE species were mined using diagnostic fragmentation filtering by searching 13C-TrEnDi-modified headgroups with m/z 199 (PC) and 202 (PE). Identities of 25 PC and 10 PE species were assigned after comparing to predicted masses from the Lipid Maps Structure Database with no false positive identifications observed; neutral lipids could still be annotated after derivatization. Collision energies from 16 to 52 eV were examined, resulting in three additional class-specific fragment ions emerging, as well as a combined sn-1/sn-2 fragment ion, allowing sum-composition level annotations to be assigned. Using the Lipid Blast templates, a NIST-compatible 13C-TrEnDi database was produced based on fragmentation spectra observed at 36 eV and tested on HEK 293T cell lipid extracts, identifying 47 PC and 24 PE species, representing a 1.8-fold and 2.2-fold increase in annotations, respectively. The 13C-TrEnDi database is freely available, MS vendor-independent, and widely compatible with MS data processing pipelines, increasing the throughput and accessibility of TrEnDi for lipidomics applications.


Assuntos
Diazometano , Espectrometria de Massas em Tandem , Espectrometria de Massas em Tandem/métodos , Diazometano/química , Fosfatidilcolinas/química
5.
J Am Soc Mass Spectrom ; 34(5): 948-957, 2023 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-37132245

RESUMO

Glyphosate (GLY), a synthetic, nonselective systemic herbicide that is particularly effective against perennial weeds, is the most used weedkiller in the world. There are growing concerns over GLY accumulation in the environment and the attendant human health-associated risks, and despite increased attention in the media, GLY and its breakdown product aminomethylphosphonic acid (AMPA) remain elusive to many analytical strategies. Chemical derivatization coupled with high-performance liquid chromatography-mass spectrometry (HPLC-MS) addresses the challenge of quantifying low levels of GLY and AMPA in complex samples. Here we demonstrate the use of in situ trimethylation enhancement using diazomethane (iTrEnDi) to derivatize GLY and AMPA into permethylated products ([GLYTr]+ and [AMPATr]+, respectively) prior to analysis via HPLC-MS. iTrEnDi produced quantitative yields and resulted in a 12-340-fold increases in HPLC-MS-based sensitivity for [GLYTr]+ and [AMPATr]+, respectively, compared with underivatized counterparts. The limits of detection of derivatized compounds were found to be 0.99 ng/L for [GLYTr]+ and 1.30 ng/L for [AMPATr]+, demonstrating significant sensitivity improvements compared to previously established derivatization techniques. iTrEnDi is compatible with the direct derivatization of Roundup formulations. Finally, as proof of principle, a simple aqueous extraction followed by iTrEnDi enabled the detection of [GLYTr]+ and [AMPATr]+ on the exterior of field-grown soybeans that were sprayed with Roundup. Overall, iTrEnDi ameliorates issues relating to low proton affinity and chromatographic retention, boosting HPLC-MS-based sensitivity and enabling the elucidation of elusive analytes such as GLY and AMPA within agricultural systems.


Assuntos
Herbicidas , Espectrometria de Massas em Tandem , Humanos , Cromatografia Líquida de Alta Pressão/métodos , Herbicidas/análise , Herbicidas/metabolismo , Espectrometria de Massas em Tandem/métodos , Glifosato
6.
Front Psychol ; 12: 644763, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33935900

RESUMO

Parks and town squares can play an important role by offering spaces for cognitive restorativeness in urban contexts. Therefore, it is important that these spaces be designed in a way that encourages restorativeness. Indeed, their perceived quality should motivate users to stay and take advantage of them. Yet, it is not clear whether perceptions as to the quality of these spaces is relevant in promoting restorativeness. Thus, the aim of this study is to analyze whether elements of environmental quality perceived by users of public spaces favor restorativeness both in parks and squares. Environmental and social aspects are taken into consideration, since restorative experiences involve cognitive and physiological recovery, as well as a component of interaction with the environment. In this research, 519 users of 32 urban public spaces-town squares and parks-on the island of Tenerife (Spain) participated. Participants evaluated these spaces using four dimensions that focused on spaces' perceived environmental quality: design of spaces, care of spaces, social interaction, and presence of sensorial elements. Additionally, we evaluated the perceived restorativeness of each space. The results showed that the design of spaces, care of the spaces, social interaction, and presence of sensorial elements explain the variance in perceived restorativeness, although with different weights for parks and squares. We found that perceived quality of a space is a key predictor of its restorativeness. This means that maintaining parks and town squares is a relevant task given that they contribute to reducing cognitive overload, increasing sustainability, and facilitating health care in urban settings.

7.
Anal Chem ; 93(2): 1084-1091, 2021 01 19.
Artigo em Inglês | MEDLINE | ID: mdl-33300778

RESUMO

Trimethylation enhancement using diazomethane (TrEnDi) is a derivatization technique that significantly enhances the signal intensity of glycerophospholipid species in mass spectrometry (MS) and tandem mass spectrometry (MS/MS) analyses. Here, we describe a novel apparatus that is able to conduct in situ TrEnDi (iTrEnDi) by generating and immediately reacting small amounts of gaseous diazoalkane with analyte molecules. iTrEnDi allows complete and rapid methylation of phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidic acid (PA), and sphingomyelin (SM) in a safe manner by removing any need for direct handling of dangerous diazoalkane solutions. iTrEnDi-modified PC ([PCTr]+) and PE ([PETr]+) showed similar sensitivity enhancements and fragmentation patterns compared to our previously reported methodology. iTrEnDi yielded dimethylated PA ([PATr]), which exhibited dramatically improved chromatographic behavior and a 14-fold increase in liquid chromatography MS (LCMS) sensitivity compared to unmodified PA. In comparison to in-solution-based TrEnDi, iTrEnDi demonstrated a modest decrease in sensitivity, likely due to analyte losses during handling. However, the enhanced safety benefits of iTrEnDi coupled with its ease of use and capacity for automation, as well as its accommodation of more-reactive diazoalkane species, vastly improve the accessibility and utility of this derivatization technique. Finally, as a proof of concept, iTrEnDi was used to produce diazoethane (DZE), a more-reactive diazoalkane than diazomethane. Reaction between DZE and PC yielded ethylated [PCTr]+, which fragmented via MS/MS to produce a high-intensity characteristic fragment ion, enabling a novel and highly sensitive precursor ion scan.

8.
Org Biomol Chem ; 15(27): 5772-5780, 2017 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-28660262

RESUMO

The post-functionalization of a chiral catalyst offers the advantage of providing it with additional physical characteristics that, together with its enantioselective capacity, increase its overall synthetic value. Taking advantage of the modularity and polyfunctionality of carbohydrate-derived ligands, herein we report the synthesis of two mixed P/S catalysts functionalized with a pyrene group through the 6 position of the sugar by carbon chains of different lengths. Using the hydrogenation of methyl (Z)-α-acetamidocinnamate as the model reaction has shown that the proximity of the pyrenyl group to the catalytic center is detrimental to the activity and enantioselectivity of the hydrogenation process, the most efficient catalyst being the complex derived from pyrenebutyric acid 12. The study of the supramolecular π-π interaction of the most active complex 12 with SWCNTs by UV-Vis spectroscopy shows, that in ethyl acetate complex 12 is totally adsorbed onto the SWCNT surface, while in methylene chloride there is an equilibrium between the adsorbed and the free form of the complex, allowing the use of complex 12 and SWCNTs in a catch and release process. Interestingly, it has been determined that the nanocatalyst 12/SWCNT is more enantioselective than complex 12 alone, affording (S)-N-acetylphenyl alanine 16 in quantitative yield and 96% ee.


Assuntos
Carboidratos/química , Cinamatos/química , Compostos Organofosforados/química , Fenilalanina/análogos & derivados , Pirenos/química , Ródio/química , Catálise , Hidrogenação , Ligantes , Estrutura Molecular , Fenilalanina/síntese química , Fenilalanina/química , Estereoisomerismo
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