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1.
Soft Matter ; 17(43): 9916-9925, 2021 Nov 10.
Artículo en Inglés | MEDLINE | ID: mdl-34672316

RESUMEN

The existing literature on the rise velocities of air bubbles in aqueous surfactant solutions adsorbing at the water-air interface focuses mainly on large bubbles (D > 1.2 mm). In addition, due to the way the bubbles in rising bubble experiments are formed, their size is dependent on interfacial tension (the lower the interfacial tension the smaller the bubble). In this paper, smaller air bubbles (D < 505 ± 3 µm) are used to investigate the effect of the bubble size on the detection of two flotation frothers of different adsorption kinetics via bubble rise velocity measurements. We use an alternative method for bubble generation, allowing us to compare the rise velocity of bubbles of the same size in solutions of frothers of varying bulk concentration. The approach taken (ensuring consistent bubble size) ascertains that the buoyancy force component is kept constant when comparing the different solutions. As a consequence, any variations in the bubble rise velocity can be related to changes in the hydrodynamic drag force acting on a rising bubble. The interfacial behavior of frothers, i.e. the adsorption kinetics, interfacial activity and the maximum amount of molecules adsorbed at the interface, are determined from interfacial tension measurements and adsorption isotherms. The differences in the degree of tangential immobilisation caused by two different frothers are discussed in the context of differences in the structure of the dynamic adsorption layer, which is formed during the bubble rise.

2.
Bioorg Med Chem Lett ; 31: 127663, 2021 01 01.
Artículo en Inglés | MEDLINE | ID: mdl-33160025

RESUMEN

A series of inhibitors of Autotaxin (ATX) have been developed from a high throughput screening hit, 1a, which shows an alternative binding mode to known catalytic site inhibitors. Selectivity over the hERG channel and microsomal clearance were dependent on the lipophilicity of the compounds, and this was optimised by reduction of clogD whilst maintaining high affinity ATX inhibition. Compound 15a shows good oral exposure, and concentration dependent inhibition of formation of LPA in vivo, as shown in pharmacokinetic-pharmacodynamic (PK/PD) experiments.


Asunto(s)
Amidas/farmacología , Cinamatos/farmacología , Desarrollo de Medicamentos , Inhibidores Enzimáticos/farmacología , Hidrolasas Diéster Fosfóricas/metabolismo , Tetrazoles/farmacología , Amidas/síntesis química , Amidas/química , Animales , Cinamatos/síntesis química , Cinamatos/química , Relación Dosis-Respuesta a Droga , Inhibidores Enzimáticos/síntesis química , Inhibidores Enzimáticos/química , Humanos , Ratones , Modelos Moleculares , Estructura Molecular , Ratas , Relación Estructura-Actividad , Tetrazoles/síntesis química , Tetrazoles/química
3.
Biotechnol Bioeng ; 117(11): 3379-3389, 2020 11.
Artículo en Inglés | MEDLINE | ID: mdl-32667685

RESUMEN

Many manufacturers of biopharmaceuticals are moving from batch to continuous processing. While this approach offers advantages over batch processing, demonstration of viral clearance for continuous processes is challenging. Fluctuating output from a continuous process chromatography column results in a nonhomogeneous load for the subsequent column and must be considered when designing viral clearance studies. One approach to clearance studies is to downscale the connected unit operations and introduce virus by in-line spiking. This is challenging to be implemented at the contract research organization performing the clearance study given the complexity of systems and level of expertise required. Alternately, each unit operation could be evaluated in traditional batch mode but the spiking and loading conditions be modified to mimic the variance introduced by the transition between two connected columns. Using a standard chromatography system, we evaluated a flow-through anion exchange chromatography step in a monoclonal antibody (mAb) manufacturing process using five different methods to introduce the virus to the column. Our data show that whether the virus or the mAbs were introduced in concentrated peaks, or as a homogeneous batch, the clearance of mouse minute virus was similar. This study introduces an alternative way to evaluate viral clearance in a continuous process and demonstrates the robustness of anion exchange chromatography unit operating in continuous processing.


Asunto(s)
Anticuerpos Monoclonales , Técnicas de Cultivo de Célula/métodos , Cromatografía por Intercambio Iónico/métodos , Virus/aislamiento & purificación , Anticuerpos Monoclonales/análisis , Anticuerpos Monoclonales/metabolismo , Productos Biológicos/análisis , Productos Biológicos/metabolismo , Productos Biológicos/normas , Reactores Biológicos
4.
Mar Drugs ; 18(11)2020 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-33114688

RESUMEN

Biopolymer polyelectrolyte multilayers are a commonly studied soft matter system for wound healing applications due to the biocompatibility and beneficial properties of naturally occurring polyelectrolytes. In this work, a popular biopolymer, chitosan, was combined with the lesser known polysaccharide, fucoidan, to create a multilayer film capable of sequestering growth factor for later release. Fucoidan has been shown to act as a heparin-mimic due to similarities in the structure of the two molecules, however, the binding of fibroblast growth factor-2 to fucoidan has not been demonstrated in a multilayer system. This study assesses the ability of fucoidan to bind fibroblast growth factor-2 within a fucoidan/chitosan polyelectrolyte multilayer structure using attenuated total internal reflectance infrared spectroscopy and quartz crystal microbalance with dissipation monitoring. The fibroblast growth factor-2 was sequestered into the polyelectrolyte multilayer as a cationic layer in the uppermost layers of the film structure. In addition, the diffusion of fibroblast growth factor-2 into the multilayer has been assessed.


Asunto(s)
Quitosano/química , Factor 2 de Crecimiento de Fibroblastos/química , Polisacáridos/química , Biopolímeros/química , Polielectrolitos/química , Espectroscopía Infrarroja por Transformada de Fourier/métodos
5.
Langmuir ; 35(33): 10734-10743, 2019 08 20.
Artículo en Inglés | MEDLINE | ID: mdl-31362506

RESUMEN

Adsorption of carboxymethyl cellulose (CMC) in aqueous solution onto a titania nanoparticle film has been studied using in situ attenuated total reflectance infrared spectroscopy (ATR-IR). CMC was adsorbed onto the positively charged titania surface in neutral, partially charged, and fully charged state. The response of the adsorbed polyelectrolyte layer was monitored upon changing the electrolyte pH and ionic strength. The degree of dissociation of the CMC increased upon adsorption onto the titania surface and changed with the surface coverage. Ionic strength change was observed to influence the degree of dissociation of the adsorbed CMC similar as when in solution. No significant peak shifts were observed in the spectrum of the adsorbed CMC during adsorption or in response to changing solution conditions; therefore, inner-sphere complexation between the carboxyl groups and the titania could not be confirmed. The effect of ion identity on the adsorption process was studied using soft and hard cations and mono- and divalent cations. The presence of a divalent counterion was observed to cause changes in the carboxymethyl vibrations, which can be related to formation of intra- or interchain linkages.

6.
Langmuir ; 34(45): 13481-13490, 2018 11 13.
Artículo en Inglés | MEDLINE | ID: mdl-30343576

RESUMEN

Polyethoxylated (PEO) surfactant adsorption to silica under aqueous conditions is an important physical process in a multitude of industries. Consequently, a considerable number of spectroscopic and other studies have been carried out to ascertain the molecular/structural details of the adsorbed surfactant and the kinetics of PEO surfactant adsorption. However, the use of infrared spectroscopy to probe surfactant adsorption at the silica/aqueous solution interface has been limited because of the instability of silica particle films under aqueous conditions and the opacity of silicon prisms below 1300 cm-1 typically employed for these studies. The work presented here provides infrared spectroscopic measurements of silica particle films formed from differing suspension pH on a diamond internal reflection prism to probe silica particle film stability as a function of pH. The films formed from a suspension pH of 2.5 were found to be the most stable owing to a sol-gel transition of the colloidal suspension upon drying and the reduction in electrostatic repulsion between silica nanoparticles, creating a tightly packed nanoparticle film. Colloid probe atomic force microscopy (CP-AFM) was used to confirm the alteration of surface forces between silica nanoparticles as a function of pH. Particle films from silica suspensions of pH 2.5 were formed in situ on an attenuated total reflection infrared diamond prism and used to probe Triton X-100 adsorption from an aqueous solution. The obtained infrared spectra revealed a critical surface aggregation concentration at a solution concentration of 0.14 mmol L-1, Triton X-100 forms discrete micelles at the silica surface, and the PEO head group preferentially adopts a helical conformation. Most intriguingly, a breakup of the silica particle film was observed at the critical micelle concentration of the surfactant. This is due to the repulsive steric forces arising from the interactions between the PEO corona of the surfactant micelles formed at the silica surface, as confirmed by the CP-AFM measurements.

7.
Bioorg Med Chem Lett ; 27(13): 2926-2930, 2017 07 01.
Artículo en Inglés | MEDLINE | ID: mdl-28499731

RESUMEN

Gastrointestinal dysfunction as a consequence of the use of opioid analgesics is of significant clinical concern. First generation drugs to treat these opioid-induced side-effects were limited by their negative impact on opioid receptor agonist-induced analgesia. Second generation therapies target a localized, peripherally-restricted, non-CNS penetrant drug distribution of opioid receptor antagonists. Herein we describe the discovery of the N-substituted-endo-3-(8-aza-bicyclo[3.2.1]oct-3-yl)-phenol and -phenyl carboxamide series of µ-opioid receptor antagonists. This report highlights the discovery of the key µ-opioid receptor antagonist pharmacophore and the optimization of in vitro metabolic stability through the application of a phenol bioisostere. The compounds 27a and 31a with the most attractive in vitro profile, formed the basis for the application of Theravance Biopharma's multivalent approach to drug discovery to afford the clinical compound axelopran (TD-1211), targeted for the treatment of opioid-induced constipation.


Asunto(s)
Amidas/farmacología , Descubrimiento de Drogas , Fenoles/farmacología , Receptores Opioides mu/antagonistas & inhibidores , Amidas/síntesis química , Amidas/química , Animales , Relación Dosis-Respuesta a Droga , Cobayas , Humanos , Estructura Molecular , Fenoles/síntesis química , Fenoles/química , Receptores Opioides delta/antagonistas & inhibidores , Receptores Opioides delta/metabolismo , Receptores Opioides mu/metabolismo , Relación Estructura-Actividad
8.
Phys Chem Chem Phys ; 19(35): 23790-23801, 2017 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-28664960

RESUMEN

Two different fucoidan polymers (unfractionated Fucus vesiculosus fucoidan, and fractionated low molecular weight Fucus vesiculosus fucoidan) have been used to create substrates for protein adsorption studies. Polyelectrolyte multilayers were formed using the fucoidans (polyanions) with chitosan as the corresponding polycation. Multilayer formation was studied using zeta potential measurements, quartz crystal microbalance with dissipation monitoring (QCM-D) and attenuated total reflectance (ATR) FTIR spectroscopy. The formation studies reveal that the low molecular weight (LMW) fucoidan produces a less hydrated multilayer, with a significantly increased adsorbed mass, and with fucoidan as the diffusing species during formation. Protein adsorption studies using bovine serum albumin (BSA) were undertaken for solution conditions designed to mimic biological conditions, and to minimise the role of electrical double layer forces in influencing adsorption. Under these conditions, and as revealed by ATR FTIR spectroscopy, BSA is seen to adsorb less substantially to multilayers formed with the LMW fucoidan, and to cause extraction/stripping of the LMW fucoidan from the multilayer. FTIR spectra reveal that the protein adopts a different conformation when adsorbed to the LMW fucoidan multilayer, both relative to the protein in solution and when adsorbed at the surface of the multilayer formed from unfractionated fucoidan.

9.
Phys Chem Chem Phys ; 19(35): 23781-23789, 2017 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-28664946

RESUMEN

We studied the interfacial mechanical properties of polyelectrolyte multilayer assemblies of poly(diallylamine hydrochloride) (PAH) and poly(4-styrenesulfonate)sodium salt (PSS) at the air-water interface using axisymmetric drop shape analysis (ADSA) during hydrostatic inflation as a function of aqueous salt concentration and two different polyanion molecular weights (Mw ∼ 13 and 70 kDa). Surface elastic moduli (Gs) ranged from 50 to 300 mN m-1. Using the measured film thickness, the bulk moduli (G) ranged from 10 to 90 MPa consistent with elastomeric solids. This solid-like interface was evidenced by a systematic departure of the inflated shape from the Young-Laplace equation, which assumes a liquid-like interface. Surface elastic moduli increased and bulk elastic moduli decreased with increasing nanomembrane transverse dimension, and multilayers with the lower molecular weight anion were more transversely compact than those of higher molecular weight and displayed a larger elastic modulus. The bulk moduli of both types of multilayer assemblies asymptotically approach a constant value for films with more than two bilayers of polyelectrolyte, consistent with the observed transition from a 'glassy' to 'rubbery' state. Both types of multilayer assemblies displayed plasticization with increasing sodium chloride concentration in the adjoining aqueous phase, i.e. saloplasticity, and exhibited a transition from elastic to plastic response to deformation. The restored mobility of the polyelectrolyte resulting from the shift from intrinsic to extrinsic charge complexation, restores fluidity to the interface and is evidenced by experimental observation of a liquid-like interface when loaded. The higher molecular weight polyanion multilayers plasticized at lower salt concentrations suggesting that the lower melting point of the higher molecular weight polyanion assembly is attributable to a lesser extent of electrostatic cross-linking underscoring the unconventional dependence of molecular weight on saloplasticity in strongly dissociated polyelectrolytes.

10.
Langmuir ; 32(6): 1568-76, 2016 Feb 16.
Artículo en Inglés | MEDLINE | ID: mdl-26804934

RESUMEN

Silica has been frequently studied using infrared and Raman spectroscopy due to its importance in many practical contexts where its surface chemistry plays a vital role. The majority of these studies have utilized chemical-vapor-deposited films in vacuo after high-temperature calcination. However, room-temperature hydration and dehydration of thin silica particle films has not been well characterized in spite of the importance of such films as substrates for polymer and surfactant adsorption. The present study has utilized ATR-IR spectroscopy and thin silica particle films exposed to varying humidity to clearly show reversible conversion between surface siloxanes and hydrogen-bonded silanols without the need for semiempirical peak deconvolution. The IR spectra from corresponding hydration experiments on deuterated silica films has confirmed the vibrational mode assignments. The variation of humidity over silica films formed from silica suspensions of differing pH gave IR spectra consistent with the change in the relative populations of siloxide to silanol surface groups. In addition, total internal reflection Raman spectroscopy has been used to provide further evidence of room-temperature dehydroxylation, with spectral evidence for the presence of three-membered siloxane rings when films are dehydrated under argon. The confirmation of room-temperature siloxane-to-silanol interconversion is expected to benefit understanding in many silica surface chemical contexts.

11.
Langmuir ; 31(41): 11249-59, 2015 Oct 20.
Artículo en Inglés | MEDLINE | ID: mdl-26421938

RESUMEN

The formation of fucoidan/chitosan-based polyelectrolyte multilayers (PEMs) has been studied with in situ Fourier transform infrared (FTIR) spectroscopy. Attenuated total reflectance (ATR) FTIR spectroscopy has been used to follow the sequential build-up of the multilayer, with peaks characteristic of each polymer being seen to increase in intensity with each respective adsorption stage. In addition, spectral processing has allowed for the extraction of spectra from individual adsorbed layers, which have been used to provide unambiguous determination of the adsorbed mass of the PEM at each stage of formation. The PEM was seen to undergo a transition in growth regimes during build-up: from supra-linear to linear. In addition, the wettability of the PEM has been probed at each stage of the build-up, using the captive bubble contact angle technique. The contact angles were uniformly low, but showed variation in value depending on the nature of the outer polymer layer, and this variation correlated with the overall percentage hydration of the PEM (determined from FTIR and quartz crystal microbalance data). The nature of the hydration water within the polyelectrolyte multilayer has also been studied with FTIR spectroscopy, specifically in situ synchrotron ATR FTIR microscopy of the multilayer confined between two solid surfaces. The acquired spectra have enabled the hydrogen bonding environment of the PEM hydration water to be determined. The PEM hydration water is seen to have an environment in which it is subject to fewer hydrogen bonding interactions than in bulk electrolyte solution.


Asunto(s)
Quitosano/química , Polímeros/síntesis química , Polisacáridos/química , Electrólitos/síntesis química , Electrólitos/química , Estructura Molecular , Polímeros/química , Espectroscopía Infrarroja por Transformada de Fourier , Agua/química
12.
Soft Matter ; 11(3): 587-99, 2015 Jan 21.
Artículo en Inglés | MEDLINE | ID: mdl-25515526

RESUMEN

The adsorption of carboxymethylcellulose (CMC), and the subsequent effect on bubble-surface interactions, has been studied for a graphite surface. CMC adsorbs on highly oriented pyrolytic graphite (HOPG) in specific patterns: when adsorbed from a solution of low concentration it forms stretched, isolated and sparsely distributed chains, while upon adsorption from a solution of higher concentration, it forms an interconnected network of multilayer features. The amount and topography of the adsorbed CMC affect the electrical properties as well as the wettability of the polymer-modified HOPG surface. Adsorption of CMC onto the HOPG surface causes the zeta potential to be more negative and the modified surface becomes more hydrophilic. This increase in both the absolute value of zeta potential and the surface hydrophilicity originates from the carboxymethyl groups of the CMC polymer. The effect of the adsorbed polymer layer on wetting film drainage and bubble-surface/particle attachment was determined using high speed video microscopy to monitor single bubble-surface collision, and single bubble Hallimond tube flotation experiments. The time of wetting film drainage and the time of three-phase contact line spreading gets significantly longer for polymer-modified HOPG surfaces, indicating that the film rupture and three-phase contact line expansion were inhibited by the presence of polymer. The effect of longer drainage times and slower dewetting correlated with reduced flotation recovery. The molecular kinetic (MK) model was used to quantify the effect of the polymer on dewetting dynamics, and showed an increase in the jump frequency for the polymer adsorbed at the higher concentration.


Asunto(s)
Carboximetilcelulosa de Sodio/química , Grafito/química , Adsorción , Simulación por Computador , Microfluídica , Resistencia al Corte , Electricidad Estática , Humectabilidad
13.
Soft Matter ; 11(11): 2110-24, 2015 Mar 21.
Artículo en Inglés | MEDLINE | ID: mdl-25599229

RESUMEN

Fucoidan is a sulfated polysaccharide that is extracted primarily from seaweed. The polymer contains a natural variation in chemistry based upon the species of seaweed from which it is extracted. We have used two different fucoidans from two different seaweed species (Fucus vesiculosus - FV; and Undaria pinnatifida - UP) as polyanions for the formation of polysaccharide-based polyelectrolyte multilayers (PEMs), to determine if the chemistry of different fucoidans can be chosen to fine-tune the structure of the polymer film. Partially acetylated chitosan was chosen as the polycation for the work, and the presented data illustrate the effect of secondary hydrogen bonding interactions on PEM build-up and properties. Ellipsometry and quartz crystal microbalance with dissipation monitoring (QCM-D) measurements performed during film build-up enabled detailed measurements of layer thickness, adsorbed mass, and the dynamics of the multilayer formation process. High quality atomic force microscopy (AFM) images revealed the differences in morphology of the PEMs formed from the two fucoidans, and allowed for a more direct layer thickness measurement. X-ray photoelectron spectroscopy (XPS) confirmed the chemistry of the films, and an indication of the altered interactions between chitosan and fucoidan with variation in fucoidan type, but also with layer number. Distinct differences were observed between multilayers formed with the two fucoidans, with those constructed using UP having thinner, denser, less hydrated layers than those constructed using FV. These differences are discussed in the context of their varied chemistry, primarily their difference in molecular weight and degree of acetylation.


Asunto(s)
Electrólitos/química , Polisacáridos/química , Quitosano/química , Módulo de Elasticidad , Fucus/química , Microscopía de Fuerza Atómica , Peso Molecular , Espectroscopía de Fotoelectrones , Tecnicas de Microbalanza del Cristal de Cuarzo
14.
Phys Chem Chem Phys ; 17(6): 4199-209, 2015 Feb 14.
Artículo en Inglés | MEDLINE | ID: mdl-25567107

RESUMEN

Gold was exposed to ethanol solutions containing 0.1 wt% 1-hexyl-3-methyl-imidazolium bis(trifluoromethanesulfonyl)imide (HMIM NTf2), an ionic liquid (IL). The resulting adsorbed layers were interrogated using X-ray photoelectron spectroscopy (XPS - both conventional and synchrotron-based) and spectroscopic ellipsometry. Ellipsometry indicated that the adsorbed layer thickness was smaller than the size of an IL ion pair, with an average determined layer thickness of 0.15 nm. This value indicates that the adsorbed layer on gold is most likely patchy. Conventional XPS revealed that the IL adsorbs irreversibly to gold, with equal amounts of anion and cation in the adsorbed layer. High signal-to-noise synchrotron XPS spectra permitted detailed deconvolution of the S 2p and N 1s peaks for the IL-treated gold, providing more information on adsorbed layer composition and structure. Spectra acquired as a function of X-ray exposure time indicate that non-interacting physisorbed IL components are preferentially removed at the expense of surface bound components, and that anion and cation are both present in the surface bound layer, and also in the layer above. A model structure for the IL adsorbed on gold is proposed.

15.
Langmuir ; 30(40): 11975-84, 2014 Oct 14.
Artículo en Inglés | MEDLINE | ID: mdl-25232682

RESUMEN

The adsorption of carboxymethylcellulose polymers on molybdenite was studied using spectroscopic ellipsometry and atomic force microscopy imaging with two polymers of differing degrees of carboxyl group substitution and at three different electrolyte conditions: 1 × 10(-2) M KCl, 2.76 × 10(-2) M KCl, and simulated flotation process water of multicomponent electrolyte content, with an ionic strength close to 2.76 × 10(-2) M. A higher degree of carboxyl substitution in the adsorbing polymer resulted in adsorbed layers that were thinner and with more patchy coverage; increasing the ionic strength of the electrolyte resulted in increased polymer layer thickness and coverage. The use of simulated process water resulted in the largest layer thickness and coverage for both polymers. The effect of the adsorbed polymer layer on bubble-particle attachment was studied with single bubble-surface collision experiments recorded with high-speed video capture and image processing and also with single mineral molybdenite flotation tests. The carboxymethylcellulose polymer with a lower degree of substitution resulted in almost complete prevention of wetting film rupture at the molybdenite surface under all electrolyte conditions. The polymer with a higher degree of substitution prevented rupture only when adsorbed from simulated process water. Molecular kinetic theory was used to quantify the effect of the polymer on the dewetting dynamics for collisions that resulted in wetting film rupture. Flotation experiments confirmed that adsorbed polymer layer properties, through their effect on the dynamics of bubble-particle attachment, are critical to predicting the effectiveness of polymers used to prevent mineral recovery in flotation.

16.
Bioorg Med Chem Lett ; 24(17): 4341-7, 2014 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-25065493

RESUMEN

The optimisation of two series of 4-hydroxybenzothiazolone derived ß2-adrenoceptor agonists, bearing α-substituted cyclopentyl and ß-phenethyl amino-substituents, as inhaled long-acting bronchodilators is described. Analogues were selected for synthesis using a lipophilicity based hypothesis to achieve the targeted rapid onset of action in combination with a long duration of action. The profiling of the two series led to identification of the α-substituted cyclopentyl analogue 2 as the optimal compound with a comparable profile to the inhaled once-daily long-acting ß2-adrenoceptor agonist indacaterol. On the basis of these data 2 was promoted as the backup development candidate to indacaterol from the Novartis LABA project.


Asunto(s)
Agonistas de Receptores Adrenérgicos beta 2/administración & dosificación , Agonistas de Receptores Adrenérgicos beta 2/farmacología , Benzotiazoles/administración & dosificación , Benzotiazoles/farmacología , Receptores Adrenérgicos beta 2/metabolismo , Administración por Inhalación , Agonistas de Receptores Adrenérgicos beta 2/química , Animales , Benzotiazoles/química , Relación Dosis-Respuesta a Droga , Cobayas , Estructura Molecular
17.
Phys Chem Chem Phys ; 16(45): 25143-51, 2014 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-25330994

RESUMEN

The adsorption of poly(N-isopropyl acrylamide) (PNIPAM) onto talc from aqueous solutions has been studied using the in situ methodology of particle film attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy. PNIPAM was observed to adsorb significantly onto the talc particle film at a temperature below its lower critical solution temperature (LCST). Peak shifts were seen in the adsorbed layer FTIR spectrum that match those observed when PNIPAM solution is heated above its LCST. This observation indicates that adsorption causes a conformational re-arrangement similar to that seen when PNIPAM undergoes a coil-to-globule transition, in this case presumably induced by hydrophobic interactions between PNIPAM and the talc basal plane surface. The kinetics of adsorption are seen to be complex, with potential influences of conformational rearrangement and differential adsorption kinetics for the two dominant surface regions of talc particles. The adsorbed PNIPAM was seen to be exceptionally resistant to removal, with no desorption occurring when a background electrolyte solution was flowed over the adsorbed layer. Spectra acquired of the adsorbed polymer layer heated above the LCST reveal that a further conformational rearrangement takes place for the adsorbed layer, finalizing the transition from coil-to-globule that was initiated by the interaction with the mineral surface.

18.
Phys Chem Chem Phys ; 16(40): 22409-17, 2014 Oct 28.
Artículo en Inglés | MEDLINE | ID: mdl-25226281

RESUMEN

We report on the loading and release of curcumin (a hydrophobic polyphenol with anti-inflammatory and anti-bacterial properties) from polyelectrolyte multilayers composed of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium 4-styrenesulfonate) (PSS). We have used the in situ techniques of attenuated total reflectance (ATR) FTIR spectroscopy and quartz crystal microbalance with dissipation monitoring (QCM-D) to study the formation of the PEM and the incorporation of curcumin, providing direct evidence of the incorporation, in terms of molecular vibrations and gravimetric detection. The release of curcumin was followed using ex situ measurements of UV-visible spectroscopy of PEM films on quartz plates, in addition to in situ ATR FTIR measurements. Release was studied as a function of salt concentration of the release solution (0.001 M NaCl; 1 M NaCl). UV-visible spectroscopy indicated that salt concentration of the release solution had a major impact on release rates, with higher salt giving faster/more extensive release. However, prolonged timescale immersion and monitoring with UV-visible spectroscopy indicated that sample dehydration/rehydration cycling (required to measure UV absorbance) was responsible for the release of curcumin, rather than immersion time. In situ measurements of release kinetics with ATR FTIR confirmed that release does not occur spontaneously while the multilayer remains hydrated.


Asunto(s)
Polietilenos/química , Polímeros/química , Compuestos de Amonio Cuaternario/química , Ácidos Sulfónicos/química , Electrólitos/química , Interacciones Hidrofóbicas e Hidrofílicas , Estructura Molecular , Tecnicas de Microbalanza del Cristal de Cuarzo , Espectroscopía Infrarroja por Transformada de Fourier
19.
Psychol Trauma ; 2024 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-38227441

RESUMEN

OBJECTIVES: The study investigated the relationship between psychological distress, alcohol use, the three fears of compassion (i.e., to self, from others, and to others), facilitators and inhibitors of compassion (self-reassurance, shame, and self-criticizing), and the three flows of compassion (to self, to others, and from others) on moral injury (MI) in military veterans. METHOD: A total of 127 participants (81.9% male, Mage = 51.24, SD = 13.98) completed measures of MI, psychological distress, alcohol use, shame, fears of compassion, self-criticizing and self-reassurance, and the three flows of compassion. Bivariate correlations and a hierarchical multiple regression were conducted to determine relationships between psychological distress, alcohol use, and the facets of compassion and MI, and whether psychological distress, alcohol use, and the facets of compassion predicted MI among veterans. RESULTS: Demographic variables of younger age and lower rank alongside psychological distress, alcohol use, and the facets of compassion were all significantly related to MI in veterans. Age, rank, psychological distress, alcohol use, and the facets of compassion did not predict MI in veterans. However, shame was found to be the biggest predictor of MI in veterans, followed by lower rank. CONCLUSION: The study supports prior research indicating MI as a shame-based presentation with younger age and lower rank posing as risk factors for MI in veterans. Additionally, the findings indicate strong relationships between the facets of compassion and MI in veterans, highlighting the potential clinical utility of including compassion within MI-based interventions. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

20.
Adv Colloid Interface Sci ; 326: 103138, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38522289

RESUMEN

This review focuses on the current understanding regarding lipid crystallisation at oil-water interfaces. The main aspects of crystallisation in bulk lipids will be introduced, allowing for a more comprehensive overview of the crystallisation processes within emulsions. Additionally, the properties of an emulsion and the impact of lipid crystallisation on emulsion stability will be discussed. The effect of different emulsifiers on lipid crystallisation at oil-water interfaces will also be reviewed, however, this will be limited to their impact on the interfacial crystallisation of monoglycerides and diglycerides. The final part of the review highlights the recent methodologies used to study crystallisation at oil-water interfaces.

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