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1.
Artículo en Inglés | MEDLINE | ID: mdl-39030314

RESUMEN

Removal of organic dyes like methylene blue (MB) from industrial effluents serves as potential source of potable water. Photocatalytic degradation using sustainable catalyst is deemed to be an affordable solution. In this work, Nd2O3/MgO nanocomposite with different compositions (1, 3, and 5wt% Nd2O3 with MgO) have been achieved using hydrothermal synthesis and characterized extensively. Interestingly, increasing Nd2O3 proportion (1-5%) enhances light absorption, and decreases band gap and electron-hole recombination. The efficacy of the photocatalysts is tested with the degradation of MB dye, through optimizing Nd2O3/MgO proportion, contact time, catalyst dose, and pH. Interestingly, control experiments reveal that 5wt% Nd2O3/MgO achieve 99.6% degradation of MB in 90 min at pH 7, compared to 88.8% with bare MgO under same condition. Kinetic data show that 5wt% Nd2O3/MgO exhibits ca. 3 times higher degradation rate compared to MgO. For the first time, our work enable MgO-based sustainable photocatalyst development with minimum (5 wt%) rare-earth combination to achieve excellent photocatalytic degradation performance.

2.
Nutr Cancer ; 74(7): 2565-2580, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35102802

RESUMEN

The current study was focused to evaluate the antioxidant and the anti-cancerous properties of Plumeria alba. Plumeria alba was chosen due to its existing medicinal values. Antioxidant assays like Superoxide radical scavenging assay, Nitrous Oxide radical scavenging assay, were performed, on the methanolic and ethyl acetate extracts of the plant, that depicts the pro-oxidant nature of the extract. Further, they were tested to check cell viability on B cell Acute Lymphoblastic Leukemia (ALL) Cell line (NALM 6), human lung cancer cell line (A549), T cell Acute Lymphoblastic Leukemia cell line (MOLT4), and PBMC isolated from normal donors utilizing MTT assay. Robust anti-proliferative activity was observed in the case of NALM 6 followed by A549, MOLT4, whereas negligible activity was observed in the case of PBMC. Intrigued by this finding, in silico docking was performed using three bioactive compounds namely Plumericine, Isoplumericine, and 13-O-p-Coumaroylplumieride, unique to Plumeria sp. They were docked against five different cyclins and Cdk proteins responsible for ALL. The compounds have shown satisfactory results and their druggability and ADMET properties were checked further. Plumercine turned out to be the most competent compound and hence can be considered as a potential leukemic drug candidate in the future.


Asunto(s)
Apocynaceae , Leucemia-Linfoma Linfoblástico de Células Precursoras , Antioxidantes , Humanos , Leucocitos Mononucleares , Extractos Vegetales/farmacología , Leucemia-Linfoma Linfoblástico de Células Precursoras/tratamiento farmacológico
3.
J Am Chem Soc ; 141(42): 16553-16558, 2019 Oct 23.
Artículo en Inglés | MEDLINE | ID: mdl-31529952

RESUMEN

High efficiency perovskite solar cells have underpinned the rapid growth of the field. However, their low device stability limits further advancement. Hygroscopic lithium bis(trifluoromethanesulfonyl)imide (Li+TFSI-) and metal electrode are the main causes of the device instability. In this work, the redox reaction between lithium-ion endohedral fullerenes and 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobi-fluorene (spiro-MeOTAD) was controlled to optimize the amount of oxidized spiro-MeOTAD and antioxidizing neutral endohedral fullerenes. Application of this mixture to metal-free carbon nanotube (CNT)-laminated perovskite solar cells resulted in 17.2% efficiency with a stability time of more than 1100 h under severe conditions (temperature = 60 °C, humidity = 70%). Such high performance is attributed to the uninhibited charge flow, no metal-ion migration, and the enhanced antioxidizing activity of the devices.

4.
Phys Chem Chem Phys ; 21(15): 8161-8169, 2019 Apr 21.
Artículo en Inglés | MEDLINE | ID: mdl-30938379

RESUMEN

We study the effect of organic cation-centered states in mixed organic-inorganic halide perovskites on the bandstructure and optical properties. Clusters of methylammonium lead iodide (MAPbI3) and bromide (MAPbBr3) and of MAPbI3 (MAPbBr3) in which an organic cation was substituted with formamidinium (FA) and guanidinium (GA) are studied with density functional theory and time-dependent density functional theory. This model permitted comparing bandstructure and optical properties with different organic cations computed with GGA and hybrid functionals. We find that while with MA and GA, cation-centered states are deep in the conduction band, with FA, organic cation-centered states are introduced within as little as 0.5 eV of the conduction band maximum, which are expected to influence electronic and optical properties of perovskites in solar cells and other optoelectronic devices. There is qualitative agreement between a GGA and a hybrid functional; however, the use of a hybrid functional leads to a slightly higher offset of the cation-centered states from the conduction band edge, a different order of electronic states, and much better localization of cation-centered states. Analysis of optical absorption spectra suggests that occupation by photoexcitation of FA-centered states and formation of transient formamidinium species is possible in both I and Br-based perovskites.

5.
J Chem Phys ; 149(4): 044114, 2018 Jul 28.
Artículo en Inglés | MEDLINE | ID: mdl-30068166

RESUMEN

We compare the performance of an approach using real frequency dependent polarizability to compute optical absorption spectra to linear-response time-dependent density functional theory (TD-DFT) for small organic dyes, oligomers of different lengths (oligothiophenes), and molecular clusters representing a molecular crystal (pentacene). For pentacene, the spectra computed with the two methods are also compared to the spectrum computed for clusters and the periodic solid using the dipole approximation. The approach based on real polarizability produces spectra in good agreement with TD-DFT for small molecules. The (artificial) redshift for longer oligomers is slightly more significant with the polarizability-based method than with TD-DFT. For pentacene clusters, TD-DFT produces reasonable spectra with a hybrid functional, but a significant redshift is introduced with a generalized gradient approximation functional due to the presence of charge transfer transitions. This problem is slightly attenuated with the polarizability-based method. The dipole approximation results in spectra much redshifted vs both TD-DFT and the polarizability-based method and in a different trend with cluster size.

6.
J Chem Phys ; 148(20): 204301, 2018 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-29865848

RESUMEN

C60 and C60 based molecules are efficient acceptors and electron transport layers for planar perovskite solar cells. While properties of these molecules are well studied by ab initio methods, those of solid C60, specifically its optical absorption properties, are not. We present a combined density functional theory-Density Functional Tight Binding (DFTB) study of the effect of solid state packing on the band structure and optical absorption of C60. The valence and conduction band edge energies of solid C60 differ on the order of 0.1 eV from single molecule frontier orbital energies. We show that calculations of optical properties using linear response time dependent-DFT(B) or the imaginary part of the dielectric constant (dipole approximation) can result in unrealistically large redshifts in the presence of intermolecular interactions compared to available experimental data. We show that optical spectra computed from the frequency-dependent real polarizability can better reproduce the effect of C60 aggregation on optical absorption, specifically with a generalized gradient approximation functional, and may be more suited to study effects of molecular aggregation.

7.
Phys Chem Chem Phys ; 19(41): 28330-28343, 2017 Oct 25.
Artículo en Inglés | MEDLINE | ID: mdl-29034938

RESUMEN

We present a systematic comparative density functional theory-density functional tight binding study of multiple derivatives of C60 and C70 with different addends, in molecular as well as solid state. In particular, effects due to fullerene size, type and number of addends, and of crystallinity on band structure, charge transport, and optical properties are investigated. These are important, in particular, for rational selection of fullerene derivatives as acceptor and electron transport layers in organic as well as planar inverted perovskite solar cells. We find that by the choice of type and number of addends, one can modulate the LUMO within 0.4 eV. Changes in the HOMO can reach 0.7 eV. Substituting C70 for C60 results in destabilization of the HOMO by about 0.1 eV for indene and quinodimethane addends and by a less significant amount for PCBM addends. The effect of C70-C60 substitution on the LUMO is of similar magnitude. A more significant change in HOMO-LUMO energy is seen for the aryl addends. On the other hand, all C70 based molecules have strong visible absorption. For most addends, the crystal packing leads to a stabilization of both the LUMO and HOMO by about ∼0.2 and ∼0.1 eV, respectively, vs. single molecules. When using bis-addends, it is also possible to enhance the visible absorption. Electron and hole transport rates are computed to vary vastly depending on the addends chosen; specifically, we compute that indene and quimodimethane addends can enhance charge transport rates while the aryl addend is predicted to result in substantially smaller mobilities of electrons and holes, vs. PC60BM. Furthermore, the -CH2 and bisaddend addition can significantly enhance the charge transfer rates for the PCBM addend.

8.
Inorg Chem ; 55(2): 558-65, 2016 Jan 19.
Artículo en Inglés | MEDLINE | ID: mdl-26700074

RESUMEN

An exciting new development in main group chemistry has been the use of a constrained, "flat", phosphorus-based complex to mediate in reactions such as the dehydrogenation of ammonia borane (AB), and the activation of the N-H bond in primary amines. Its importance is based on the fact that it shows that main group compounds, when properly designed, can be as effective as transition metal complexes for doing significant chemical transformations. What the current computational study, employing density functional theory (DFT), reveals is that a common, general mechanism exists that accounts for the behavior of the flat phosphorus compound in the different reactions that have been experimentally reported to date. This mechanism, which involves the mediation by a base as a proton transfer agent, is simpler and energetically more favorable than the previous mechanisms that have been proposed for the same reactions in the literature. It is likely that the knowledge gained from the current work about the chemical behavior of this phosphorus compound can be utilized to design new constrained phosphorus-based compounds.

9.
Langmuir ; 30(46): 13791-8, 2014 Nov 25.
Artículo en Inglés | MEDLINE | ID: mdl-25333413

RESUMEN

In this work, we have designed and synthesized a series of fatty acid amphiphiles that have the same structural skeleton but different hydrogen-bonding (H-bonding) functional groups in the hydrocarbon chain. To examine the importance of the H-bonding interaction on the formation of a one-dimensional (1D) aggregate in organic solvents, we have compared the gelation behavior of these amphiphiles in some common organic solvents at room temperature. Despite the structural similarity, the amphiphiles were observed to exhibit different gelation behavior. The organogels were characterized using conventional techniques such as field emission scanning electron microscopy, X-ray diffraction, and rheology. A systematic analysis of the FT-IR and (1)H NMR spectral data, gel melting temperatures, and mechanical strengths of the organogels in a given solvent suggested the importance of H-bonding as well as van der Waals interaction in the gelation process. In this study, we have made an attempt to estimate qualitatively the relative contribution of H-bonding and van der Waals interactions between gelator molecules forming organogels. The results suggest that strong and weaker H-bonding affects the gelation ability of gelators. However, when the H-bonding interaction is weak, an increase in van der Waals interactions can result in gelation, but when both H-bonding and van der Waals interactions are weak, that is, when the amphiphiles are liquid and semisolid, no gelation is observed. It is concluded that a balance between H-bonding and van der Waals interactions is necessary for physical gelation.


Asunto(s)
Ácidos Grasos/química , Solventes/química , Enlace de Hidrógeno
10.
Langmuir ; 29(7): 2120-7, 2013 Feb 19.
Artículo en Inglés | MEDLINE | ID: mdl-23343420

RESUMEN

A series of L-cysteine-derived double hydrocarbon chain amphiphilic gelators L-(3-alkyl-carbamoylsulfanyl)-2-(3-alkylurido)propionic acid with different hydrocarbon chain lengths (C6-C16) was designed and synthesized. These gelators efficiently gelate only aromatic solvents. The gelation ability increased with the increase of chain length up to C14, but then it dropped with further increase of chain length. The C12 and C14 derivatives also gelled ethanol/water mixtures. The gels were characterized by a number of methods, including FT-IR, NMR, and XRD spectroscopy, electron microscopy, and rheology. The amphiphiles were observed to form either flat lamellar or ribbonlike aggregates in aromatic solvents as well as in ethanol/water mixtures. The gelation in all the solvents employed was observed to be thermoreversible. The gel-to-sol transition temperature as well as mechanical strength of the organogels were observed to increase with the hydrocarbon chain length. Both types of gels of C8-C16 amphiphiles have gel-to-sol transition temperatures above the physiological temperature (310 K). FT-IR and variable temperature (1)H NMR measurements suggested that van der Waals interactions have major contribution in the gelation process. The gel-to-sol transition temperature and mechanical strength of the organogels in ethanol/water mixtures was observed to be higher than those of benzene organogel.


Asunto(s)
Cisteína/química , Etanol/química , Solventes/química , Agua/química
11.
Langmuir ; 29(21): 6467-75, 2013 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-23672543

RESUMEN

A systematic study of the importance of functional group position and type on the gelator efficiencies of structurally simple, low molecular-mass gelators is reported. Thus, the gelation abilities of a series of positional isomers of ketooctadecanoic acid (n-KSA) are compared in a wide range of liquids. The gelation abilities of the n-KSA as a function of n, the keto group position along the chain, are characterized by several structural, thermal, and rheological techniques and are compared with those of the corresponding hydroxyoctadecanoic acid isomers (n-HSA) and the parent molecule, octadecanoic acid (SA). Analyses of the gels according to the strengths of functional group interactions along the alkyl chain in terms of group position and type are made. The conclusions derived from the study indicate that gel stability is enhanced when the functional group is located relatively far from the carboxylic headgroup and when group-group interactions are stronger (i.e., hydrogen-bonding interactions are stronger in the n-HSA than dipole interactions in the n-KSA, which are stronger than the London dispersion interactions in SA). Co-crystals of the keto- and hydroxy-substituted octadecanoic acids are found to be less efficient gelators than even the ketooctadecanoic acids, due to molecular packing and limited group interactions within the gelator networks.


Asunto(s)
Ácidos Esteáricos/química , Geles/síntesis química , Geles/química , Enlace de Hidrógeno , Estructura Molecular , Ácidos Esteáricos/síntesis química , Temperatura de Transición
12.
Phys Chem Chem Phys ; 15(48): 20857-67, 2013 Dec 28.
Artículo en Inglés | MEDLINE | ID: mdl-24196023

RESUMEN

Zero dimensional cage structures containing four phenyl rings separated by imine linkers have recently been synthesized. In the current work, through a computational investigation using density functional theory (DFT), we demonstrate that modifying such cages by replacing the 2, 4, 6 carbon atoms in the phenyl rings to yield new rings, as well as replacing the imine moiety in the linker by other electronegative atoms, can yield interesting new cages that can be reactive in catalysing reactions such as the dehydrogenation of ammonia borane - an important reaction in hydrogen storage research. Specifically, it is predicted that phosphorus-nitrogen pairs (phosphorus in the 2, 4, 6 positions in the ring, nitrogen in the linker position), germanium-nitrogen and germanium-phosphorus pair combinations would lead to effective Lewis pairs that can work in tandem to dehydrogenate ammonia borane efficiently under room temperature conditions.

13.
Gels ; 9(5)2023 May 04.
Artículo en Inglés | MEDLINE | ID: mdl-37232970

RESUMEN

Endovascular embolization (EE) has been used for the treatment of blood vessel abnormalities, including aneurysms, AVMs, tumors, etc. The aim of this process is to occlude the affected vessel using biocompatible embolic agents. Two types of embolic agents, solid and liquid, are used for endovascular embolization. Liquid embolic agents are usually injectable and delivered into the vascular malformation sites using a catheter guided by X-ray imaging (i.e., angiography). After injection, the liquid embolic agent transforms into a solid implant in situ based on a variety of mechanisms, including polymerization, precipitation, and cross-linking, through ionic or thermal process. Until now, several polymers have been designed successfully for the development of liquid embolic agents. Both natural and synthetic polymers have been used for this purpose. In this review, we discuss embolization procedures with liquid embolic agents in different clinical applications, as well as in pre-clinical research studies.

14.
Res Sq ; 2023 May 03.
Artículo en Inglés | MEDLINE | ID: mdl-37205583

RESUMEN

Study objectives. Women who experienced childhood sexual abuse have higher rates of obesity, a risk factor for obstructive sleep apnea (OSA). We assessed if prior childhood sexual abuse was more common in women with OSA vs. control, with possible mediation by obesity. Methods . We studied 21 women with OSA (age mean±s.d. 59±12 years, body mass index (BMI) 33±8 kg/m 2 , respiratory event index [REI] 25±16 events/hour, Epworth Sleepiness Scale [ESS] 8±5) and 21 women without OSA (age 53±9 years, BMI 25±5 kg/m 2 , REI (in 7/21 women) 1±1 events/hour, ESS 5±3). We evaluated four categories of trauma (general trauma, physical, emotional, and sexual abuse) with the early trauma inventory self-report-short form (ETISR-SF). We assessed group differences in trauma scores with independent samples t-tests and multiple regressions. Parametric Sobel tests were used to model BMI as a mediator for individual trauma scores predicting OSA in women. Results. Early childhood sexual abuse reported on the ETISR-SF was 2.4 times more common in women with vs. without OSA ( p =0.02 for group difference). Other trauma scores were not significantly different between women with and without OSA. However, BMI was a significant mediator ( p =0.02) in predicting OSA in women who experienced childhood physical abuse. Conclusions. Childhood sexual abuse was more common in a group of women with OSA than those without OSA. Additionally, BMI was a mediator for OSA of childhood physical but not sexual abuse. There may be physiological impacts of childhood trauma in women that predispose them to OSA.

15.
J Biomed Mater Res B Appl Biomater ; 110(8): 1911-1921, 2022 08.
Artículo en Inglés | MEDLINE | ID: mdl-35262274

RESUMEN

Endovascular embolization of cerebral aneurysms is a common approach for reducing the risk of often-fatal hemorrhage. However, currently available materials used to occlude these aneurysms provide incomplete filling (coils) or require a complicated, time-consuming delivery procedure (solvent-exchange precipitating polymers). The objective of this work was to develop an easily deliverable in situ forming hydrogel that can occlude the entire volume of an aneurysm. The hydrogel is formed by mixing a solution of a temperature-responsive polymer containing pendent thiol groups (poly(NIPAAm-co-cysteamine) or poly(NIPAAm-co-cysteamine-co-JAAm)) with a solution of poly(ethylene glycol) diacrylate (PEGDA). Incorporation of hydrophilic grafts of polyetheramine acrylamide (JAAm) in the temperature-responsive polymer caused weaker physical crosslinking, facilitated faster and more complete chemical crosslinking, and increased gel swelling. One formulation (30 wt % PNCJ20 + PEGDA) could be delivered for over 220 s after mixing, formed a strong and elastic hydrogel (G' > 6000 Pa) within 30 min and once set, maintained its shape and volume in a model aneurysm under flow. This gel represents a promising candidate water-based material utilizing both physical and chemical crosslinking that warrants further investigation as an embolic agent for saccular aneurysms.


Asunto(s)
Embolización Terapéutica , Hidrogeles , Elasticidad , Embolización Terapéutica/métodos , Polietilenglicoles , Polímeros , Temperatura
16.
Sleep Med ; 97: 73-81, 2022 09.
Artículo en Inglés | MEDLINE | ID: mdl-35728308

RESUMEN

INTRODUCTION: Obstructive sleep apnea (OSA) increases sympathetic vasoconstrictor drive and reduces baroreflex sensitivity (BRS), the degree to which blood pressure changes modify cardiac output. Whether nighttime continuous positive airway pressure (CPAP) corrects BRS in the awake state in OSA remains unclear. We assessed spontaneous BRS using non-invasive continuous BP and ECG recordings at rest and during handgrip and Valsalva challenges, maneuvers that increase vasoconstrictor drive with progressively higher BP, in untreated OSA (unOSA), CPAP-treated OSA (cpOSA) and healthy (CON) participants. METHODS: In a cross-sectional study of 104 participants, 34 unOSA (age mean±std, 50.6±14.1years; Respiratory Event Index [REI] 21.0±15.3 events/hour; 22male), 31 cpOSA (49.6±14.5years; REI 23.0±14.2 events/hour; 22male; self-report 4+hours/night,5+days/week,6months), and 39 CON (42.2±15.0years; 17male), we calculated BRS at rest and during handgrip and Valsalva. Additionally, we correlated BP variability (BPV) with BRS during these protocols. RESULTS: BRS in unOSA, cpOSA and CON was, respectively (mean±sdv in ms/mmHg), at rest: 14.8±11.8, 15.8±17.0, 16.1±11.3; during handgrip 13.3±7.6, 12.7±8.4, 16.4±8.7; and during Valsalva 12.7±8.0, 11.5±6.6, 15.1±8.9. BRS was lower in cpOSA than CON for handgrip (p=0.04) and Valsalva (p=0.03). BRS was negatively correlated with BPV in unOSA during Valsalva and handgrip for cpOSA, both R=-0.4 (p=0.02). BRS was negatively correlated with OSA severity (levels: none, mild, moderate, severe) at R=-0.2 (p=0.04,n=104). CONCLUSIONS: As expected, BRS was lower and BPV higher in OSA during the pressor challenges, and disease severity negatively correlated with BRS. In this cross-sectional study, both CPAP-treated (self-reported) and untreated OSA showed reduced BRS, leaving open whether within-person CPAP improves BRS.


Asunto(s)
Presión de las Vías Aéreas Positiva Contínua , Apnea Obstructiva del Sueño , Adulto , Barorreflejo/fisiología , Presión Sanguínea/fisiología , Presión de las Vías Aéreas Positiva Contínua/métodos , Estudios Transversales , Fuerza de la Mano , Humanos , Persona de Mediana Edad , Apnea Obstructiva del Sueño/terapia , Vasoconstrictores
17.
J Clin Sleep Med ; 18(3): 825-833, 2022 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-34669569

RESUMEN

STUDY OBJECTIVES: Obstructive sleep apnea (OSA) is defined by pauses in breathing during sleep, but daytime breathing dysregulation may also be present. Sleep may unmask breathing instability in OSA that is usually masked by behavioral influences during wakefulness. A breath-hold (BH) challenge has been used to demonstrate breathing instability. One measure of breathing stability is breathing rate variability (BRV). We aimed to assess BRV during rest and in response to BH in OSA. METHODS: We studied 62 participants (31 with untreated OSA: respiratory event index [mean ± SD] 20 ± 15 events/h, 12 females, age 51 ± 14 years, body mass index [BMI] 32 ± 8 kg/m2; 31 controls: 17 females, age 47 ± 13 years; BMI 26 ± 4 kg/m2). Breathing movements were collected using a chest belt for 5 minutes of rest and during a BH protocol (60 seconds baseline, 30 seconds BH, 90 seconds recovery, 3 repeats). From the breathing movements, we calculated median breathing rate (BR) and interquartile BRV at rest. We calculated change in BRV during BH recovery from baseline. Group comparisons of OSA vs control were conducted using analysis of covariance with age, sex, and BMI as covariates. RESULTS: We found 10% higher BRV in OSA vs controls (P < .05) during rest. In response to BH, BRV increased 7% in OSA vs 1% in controls (P < .001). Resting BR was not significantly different in OSA and controls, and sex and age did not have any significant interaction effects. BMI was associated with BR at rest (P < .05) and change in BRV with BH (P < .001), but no significant BMI-by-group interaction effect was observed. CONCLUSIONS: The findings suggest breathing instability as reflected by BRV is high in OSA during wakefulness, both at rest and in response to a stimulus. Breathing instability together with high blood pressure variability in OSA may reflect a compromised cardiorespiratory consequence in OSA during wakefulness. CITATION: Pal A, Martinez F, Akey MA, et al. Breathing rate variability in obstructive sleep apnea during wakefulness. J Clin Sleep Med. 2022;18(3):825-833.


Asunto(s)
Apnea Obstructiva del Sueño , Vigilia , Adulto , Anciano , Índice de Masa Corporal , Femenino , Humanos , Persona de Mediana Edad , Respiración , Sueño/fisiología , Apnea Obstructiva del Sueño/complicaciones , Vigilia/fisiología
18.
Langmuir ; 27(7): 3401-8, 2011 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-21351761

RESUMEN

A series of amino acid-based gelators N-(n-alkylcarbamoyl)-L-alanine were synthesized, and their gelation abilities in a series of organic solvents were tested. No gelation was observed in pure solvents employed. All the amphiphilic molecules were found to form stable organogels in the solvents in the presence of a small amount of water, methanol, or urea. The volume of solvent gelled by a given amount of the gelator was observed to depend upon the volume of added water. The gelation behavior of the amphiphiles in a given solvent containing a known volume of water was compared. The effects of chirality and substitution on the acid group on the gelation ability were examined. Although the corresponding N-(n-tetradecylcarbamoyl)-DL-alanine was found to form only weak organogel in pure solvents, the achiral amphiphilic compound N-(n-tetradecylcarbamoyl)-ß-alanine, however, did not form gel in the absence of water. The methyl ester of N-(n-tetradecylcarbamoyl)-L-alanine was also observed to form gels in the same solvents, but only in the presence of water. The organogels were characterized by several techniques, including (1)H NMR, Fourier transform IR, X-ray diffraction, and field emission scanning electron microscopy. The thermal and rheological properties of the organogels were studied. The mechanical strength of the organogel formed by N-(n-tetradecylcarbamoyl)-DL-alanine was observed to increase upon the addition of water. It was concluded that water-mediated intermolecular hydrogen-bonding interaction between amphiphiles caused formation of supramolecular self-assemblies.


Asunto(s)
Geles/química , Compuestos Orgánicos/química , Solventes/química , Agua/química , Alanina , Enlace de Hidrógeno , Espectroscopía de Resonancia Magnética , Microscopía Electrónica de Rastreo , Espectroscopía Infrarroja por Transformada de Fourier , Temperatura de Transición , Difracción de Rayos X
19.
PLoS One ; 16(2): e0246368, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33600443

RESUMEN

STUDY OBJECTIVES: Brain regulation of autonomic function in obstructive sleep apnea (OSA) is disrupted in a sex-specific manner, including in the insula, which may contribute to several comorbidities. The insular gyri have anatomically distinct functions with respect to autonomic nervous system regulation; yet, OSA exerts little effect on the organization of insular gyral responses to sympathetic components of an autonomic challenge, the Valsalva. We further assessed neural responses of insular gyri in people with OSA to a static handgrip task, which principally involves parasympathetic withdrawal. METHODS: We measured insular function with blood oxygen level dependent functional MRI. We studied 48 newly-diagnosed OSA (age mean±std:46.5±9 years; AHI±std:32.6±21.1 events/hour; 36 male) and 63 healthy (47.2±8.8 years;40 male) participants. Subjects performed four 16s handgrips (1 min intervals, 80% subjective maximum strength) during scanning. fMRI time trends from five insular gyri-anterior short (ASG); mid short (MSG); posterior short (PSG); anterior long (ALG); and posterior long (PLG)-were assessed for within-group responses and between-group differences with repeated measures ANOVA (p<0.05) in combined and separate female-male models; age and resting heart-rate (HR) influences were also assessed. RESULTS: Females showed greater right anterior dominance at the ASG, but no differences emerged between OSA and controls in relation to functional organization of the insula in response to handgrip. Males showed greater left anterior dominance at the ASG, but there were also no differences between OSA and controls. The males showed a group difference between OSA and controls only in the ALG. OSA males had lower left activation at the ALG compared to control males. Responses were mostly influenced by HR and age; however, age did not impact the response for right anterior dominance in females. CONCLUSIONS: Insular gyri functional responses to handgrip differ in OSA vs controls in a sex-based manner, but only in laterality of one gyrus, suggesting anterior and right-side insular dominance during sympathetic activation but parasympathetic withdrawal is largely intact, despite morphologic injury to the overall structure.


Asunto(s)
Sistema Nervioso Autónomo/fisiopatología , Corteza Cerebral/fisiopatología , Fuerza de la Mano , Apnea Obstructiva del Sueño/fisiopatología , Adulto , Femenino , Humanos , Masculino , Persona de Mediana Edad
20.
Sci Rep ; 11(1): 12631, 2021 06 16.
Artículo en Inglés | MEDLINE | ID: mdl-34135372

RESUMEN

People with obstructive sleep apnea (OSA) often have psychological symptoms including depression and anxiety, which are commonly treated with anti-depression or anti-anxiety interventions. Psychological stress is a related symptom with different intervention targets that may also improve mental state, but this symptom is not well characterized in OSA. We therefore aimed to describe stress in relation to other psychological symptoms. We performed a prospective cross-sectional study of 103 people, 44 untreated OSA (mean ± s.d. age: 51.2 ± 13.9 years, female/male 13/31) and 57 healthy control participants (age: 46.3 ± 13.8 years, female/male 34/23). We measured stress (Perceived Stress Scale; PSS), excessive daytime sleepiness (Epworth Sleepiness Scale; ESS), depressive symptoms (Patient Health Questionnaire; PHQ-9), and anxiety symptoms (General Anxiety Disorder; GAD-7). We compared group means with independent samples t-tests and calculated correlations between variables. Mean symptom levels were higher in OSA than control, including PSS (mean ± s.d.: OSA = 15.3 ± 6.9, control = 11.4 ± 5.5; P = 0.002), GAD-7 (OSA = 4.8 ± 5.0, control = 2.1 ± 3.9; P = 0.02), PHQ-9 (OSA = 6.9 ± 6.1, control = 2.6 ± 3.8; P = 0.003) and ESS (OSA = 8.1 ± 5.3, control = 5.0 ± 3.3; P = 0.03). Similar OSA-vs-control differences appeared in males, but females only showed significant differences in PHQ-9 and ESS, not PSS or GAD-7. PSS correlated strongly with GAD-7 and PHQ-9 across groups (R = 0.62-0.89), and moderately with ESS. Perceived stress is high in OSA, and closely related to anxiety and depressive symptoms. The findings support testing stress reduction in OSA.


Asunto(s)
Ansiedad/diagnóstico , Depresión/diagnóstico , Trastornos de Somnolencia Excesiva/diagnóstico , Apnea Obstructiva del Sueño/tratamiento farmacológico , Estrés Psicológico/diagnóstico , Adulto , Anciano , Ansiedad/etiología , Estudios de Casos y Controles , Estudios Transversales , Depresión/etiología , Trastornos de Somnolencia Excesiva/etiología , Femenino , Humanos , Masculino , Persona de Mediana Edad , Estudios Prospectivos , Apnea Obstructiva del Sueño/psicología , Estrés Psicológico/etiología , Encuestas y Cuestionarios , Adulto Joven
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