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1.
Proc Natl Acad Sci U S A ; 117(42): 26053-26060, 2020 Oct 20.
Artículo en Inglés | MEDLINE | ID: mdl-33020296

RESUMEN

In the presence of Lewis acid salts, the cyclic ether, dioxolane (DOL), is known to undergo ring-opening polymerization inside electrochemical cells to form solid-state polymer batteries with good interfacial charge-transport properties. Here we report that LiNO3, which is unable to ring-open DOL, possesses a previously unknown ability to coordinate with and strain DOL molecules in bulk liquids, completely arresting their crystallization. The strained DOL electrolytes exhibit physical properties analogous to amorphous polymers, including a prominent glass transition, elevated moduli, and low activation entropy for ion transport, but manifest unusually high, liquidlike ionic conductivities (e.g., 1 mS/cm) at temperatures as low as -50 °C. Systematic electrochemical studies reveal that the electrolytes also promote reversible cycling of Li metal anodes with high Coulombic efficiency (CE) on both conventional planar substrates (1 mAh/cm2 over 1,000 cycles with 99.1% CE; 3 mAh/cm2 over 300 cycles with 99.2% CE) and unconventional, nonplanar/three-dimensional (3D) substrates (10 mAh/cm2 over 100 cycles with 99.3% CE). Our finding that LiNO3 promotes reversibility of Li metal electrodes in liquid DOL electrolytes by a physical mechanism provides a possible solution to a long-standing puzzle in the field about the versatility of LiNO3 salt additives for enhancing reversibility of Li metal electrodes in essentially any aprotic liquid electrolyte solvent. As a first step toward understanding practical benefits of these findings, we create functional Li||lithium iron phosphate (LFP) batteries in which LFP cathodes with high capacity (5 to 10 mAh/cm2) are paired with thin (50 µm) lithium metal anodes, and investigate their galvanostatic electrochemical cycling behaviors.

2.
Int J Mol Sci ; 23(23)2022 Nov 29.
Artículo en Inglés | MEDLINE | ID: mdl-36499309

RESUMEN

Temperature (T) dependent conductance G=G(T) data measured in molecular junctions are routinely taken as evidence for a two-step hopping mechanism. The present paper emphasizes that this is not necessarily the case. A curve of lnG versus 1/T decreasing almost linearly (Arrhenius-like regime) and eventually switching to a nearly horizontal plateau (Sommerfeld regime), or possessing a slope gradually decreasing with increasing 1/T is fully compatible with a single-step tunneling mechanism. The results for the dependence of G on T presented include both analytical exact and accurate approximate formulas and numerical simulations. These theoretical results are general, also in the sense that they are not limited, e.g., to the (single molecule electromigrated (SET) or large area EGaIn) fabrication platforms, which are chosen for exemplification merely in view of the available experimental data needed for analysis. To be specific, we examine in detail transport measurements for molecular junctions based on ferrocene (Fc). As a particularly important finding, we show how the present analytic formulas for G=G(T) can be utilized to compute the ratio f=Aeff/An between the effective and nominal areas of large area Fc-based junctions with an EGaIn top electrode. Our estimate of f≈0.6×10-4 is comparable with previously reported values based on completely different methods for related large area molecular junctions.


Asunto(s)
Nanotecnología , Temperatura , Electrodos
3.
Angew Chem Int Ed Engl ; 60(26): 14586-14594, 2021 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-33834585

RESUMEN

Supramolecular complexation is a powerful strategy for engineering materials in bulk and at interfaces. Metal-phenolic networks (MPNs), which are assembled through supramolecular complexes, have emerged as suitable candidates for surface and particle engineering owing to their diverse properties. Herein, we examine the supramolecular dynamics of MPNs during thermal transformation processes. Changes in the local supramolecular network including enlarged pores, ordered aromatic packing, and metal relocation arise from thermal treatment in air or an inert atmosphere, enabling the engineering of metal-oxide networks (MONs) and metal-carbon networks, respectively. Furthermore, by integrating photo-responsive motifs (i.e., TiO2 ) and silanization, the MONs are endowed with reversible superhydrophobic (>150°) and superhydrophilic (≈0°) properties. By highlighting the thermodynamics of MPNs and their transformation into diverse materials, this work offers a versatile pathway for advanced materials engineering.

4.
Biochim Biophys Acta ; 1842(1): 44-55, 2014 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-24120835

RESUMEN

Congenital cataract is the leading cause of childhood blindness worldwide. Investigations of the effects of inherited mutations on protein structure and function not only help us to understand the molecular mechanisms underlying congenital hereditary cataract, but also facilitate the study of complicated cataract and non-lens abnormities caused by lens-specific genes. In this research, we studied the effects of the V187M, V187E and R188H mutations on ßB2-crystallin structure and stability using a combination of biophysical, cellular and molecular dynamic simulation analysis. Both V187 and R188 are located at the last strand of ßB2-crystallin Greek-key motif 4. All of the three mutations promoted ßB2-crystallin aggregation in vitro and at the cellular level. These three mutations affected ßB2-crystallin quite differentially: V187M influenced the hydrophobic core of the C-terminal domain, V187E was a Greek-key motif breaker with the disruption of the backbone H-bonding network, while R188H perturbed the dynamic oligomeric equilibrium by dissociating the dimer and stabilizing the tetramer. Our results highlighted the importance of the last strand in the structural integrity, folding, assembly and stability of ß-crystallins. More importantly, we proposed that the perturbation of the dynamic equilibrium between ß-crystallin oligomers was an important mechanism of congenital hereditary cataract. The selective stabilization of one specific high-order oligomer by mutations might also be deleterious to the stability and folding of the ß-crystalllin homomers and heteromers. The long-term structural stability and functional maintenance of ß-crystallins are achieved by the precisely regulated oligomeric equilibrium.


Asunto(s)
Cristalino/química , Cadena B de beta-Cristalina/química , Secuencia de Aminoácidos , Escherichia coli/genética , Escherichia coli/metabolismo , Humanos , Enlace de Hidrógeno , Interacciones Hidrofóbicas e Hidrofílicas , Cinética , Simulación de Dinámica Molecular , Datos de Secuencia Molecular , Mutación , Pliegue de Proteína , Multimerización de Proteína , Estabilidad Proteica , Estructura Secundaria de Proteína , Estructura Terciaria de Proteína , Proteínas Recombinantes/química , Proteínas Recombinantes/genética , Solubilidad , Cadena B de beta-Cristalina/genética
5.
J Colloid Interface Sci ; 669: 1015-1021, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38759592

RESUMEN

HYPOTHESIS: The formation of adducts via urea interaction with distinct classes of surfactants (cationic, anionic, nonionic, and zwitterionic), leading to their assembly into lamellar structures and subsequent formation of hydrogels. The characteristics of these hydrogels are associated with both, the length of the alkyl chain, and the specific head group of the surfactant molecules. EXPERIMENTS: Characterization of adduct formation was conducted using Wide-Angle X-ray Scattering (WAXS), while Small-Angle X-ray Scattering (SAXS) was employed to probe the subsequent assembly into lamellar structures. The kinetics of hydrogel formation were assessed through rheological measurements and observed thermal transitions utilizing Differential Scanning Calorimetry (DSC). FINDINGS: The investigation revealed a universal propensity for hydrogel formation across all surfactant classes. The formation arises from the interactions between urea molecules via hydrogen bonding, forming adducts around the surfactant chains. In sequence, the adducts self-assemble in lamellae. This process constructs the intricate three-dimensional network characteristic of the hydrogel. Furthermore, the kinetics of hydrogel formation, and their rheological properties under equilibrated conditions, were found to be significantly influenced by the nature of the polar head group of the surfactant molecules. This is the first evidence on the formation of adducts of urea with classes of surfactants. As they are common components in cosmetic, supramolecular hydrogels have high potential to be used in formulations.

6.
Adv Mater ; 36(23): e2313393, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38573779

RESUMEN

The meta-stable active layer morphology of organic solar cells (OSCs) is identified as the main cause of the rapid burn-in loss of power conversion efficiency (PCE) during long-term device operation. However, effective strategies to eliminate the associated loss mechanisms from the initial stage of device operation are still lacking, especially for high-efficiency material systems. Herein, the introduction of molecularly engineered dimer acceptors with adjustable thermal transition properties into the active layer of OSCs to serve as supramolecular stabilizers for regulating the thermal transitions and optimizing the crystallization of the absorber composites is reported. By establishing intimate π-π interactions with small-molecule acceptors, these stabilizers can effectively reduce the trap-state density (Nt) in the devices to achieve excellent PCEs over 19%. More importantly, the low Nt associated with an initially optimized morphology can be maintained under external stresses to significantly reduce the PCE burn-in loss in devices. This research reveals a judicious approach to improving OPV stability by establishing a comprehensive correlation between material properties, active-layer morphology, and device performance, for developing burn-in-free OSCs.

7.
Polymers (Basel) ; 15(19)2023 Sep 29.
Artículo en Inglés | MEDLINE | ID: mdl-37835993

RESUMEN

This review aims to report the status of the research on polyaryletherketone-based thermoplastic blends (PAEK). PAEK are high-performance copolymers able to replace metals in many applications including those related to the environmental and energy transition. PAEK lead to the extension of high-performance multifunctional materials to target embedded electronics, robotics, aerospace, medical devices and prostheses. Blending PAEK with other thermostable thermoplastic polymers is a viable option to obtain materials with new affordable properties. First, this study investigates the miscibility of each couple. Due to different types of interactions, PAEK-based thermoplastic blends go from fully miscible (with some polyetherimides) to immiscible (with polytetrafluoroethylene). Depending on the ether-to-ketone ratio of PAEK as well as the nature of the second component, a large range of crystalline structures and blend morphologies are reported. The PAEK-based thermoplastic blends are elaborated by melt-mixing or solution blending. Then, the effect of the composition and blending preparation on the mechanical properties are investigated. PAEK-based thermoplastic blends give rise to the possibility of tuning their properties to design novel materials. However, we demonstrate hereby that significant research effort is needed to overcome the lack of knowledge on the structure/morphology/property relationships for those types of high-performance thermoplastic blends.

8.
Int J Biol Macromol ; 194: 619-625, 2022 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-34822831

RESUMEN

The physicochemical properties and structural characteristics of starches from three wheat flours with different gluten strength (S-YM20, S-ZM27, and S-ZM366) during freezing/thawing (F/T) cycles were studied. After F/T treatment, the damaged starch content of these three starches all increased, and the lowest increment of damaged starch content after 8 F/T cycles was S-ZM366; the most serious distribution of particle surface concave hole and fracture was S-YM20, followed by S-ZM27 and S-ZM366; additionally, the results of solubility, swelling power, thermal stability and pasting properties indicated S-ZM366 exhibited the strongest resistance to F/T cycles. The differences of freezing resistance among the three starches were possibly ascribed to the differences in compositions, crystallinity and microstructure among these three starches. This study provides theoretical contribution to the development of frozen dough industry from the perspective of wheat variety.


Asunto(s)
Harina/análisis , Glútenes/química , Manejo de Especímenes/métodos , Almidón/química , Triticum/metabolismo , Congelación
9.
Polymers (Basel) ; 13(9)2021 May 01.
Artículo en Inglés | MEDLINE | ID: mdl-34062773

RESUMEN

Polyetheretherketone (PEEK)/polyethersulfone (PES) blends are initially not miscible, except when the blends are prepared by solvent mixing. We propose a route to elaborate PEEK/PES blends with partial miscibility by melt mixing at 375 °C with phenolphthalein. The miscibility of blends has been examined using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMTA). When adding phenolphthalein to PEEK/PES blends, the glass transitions are shifted inward as an indication of miscibility. We suggest that phenolphthalein acts as a compatibilizer by creating cardo side groups on PEEK and PES chains by nucleophilic substitution in the melted state, although this condensation reaction was reported only in the solvent until now. In addition, phenolphthalein acts as a plasticizer for PES by decreasing its glass transition. As a consequence, the PEEK phase is softened which favors the crystallization as the increase of crystalline rate. Due to aromatic moieties in phenolphthalein, the storage modulus of blends in the glassy region is kept identical to pure PEEK. The morphological analysis by SEM pictures displays nano- to microsized PES spherical domains in the PEEK matrix with improved PEEK/PES interfacial adhesion.

10.
Food Chem ; 341(Pt 1): 128214, 2021 Mar 30.
Artículo en Inglés | MEDLINE | ID: mdl-33035855

RESUMEN

Biphasic transition is an important behavior of starch caused by heat-moisture treatment (HMT). Starch may change from typical single endotherm to biphasic endotherm (G1, G2) by HMT which corresponded to two viscosity peaks (PV1 and PV2) in pasting analysis. During PV1, remarkable disruption of birefringence occurred in the inner region of starch granules, accompanied by a decreased relative crystallinity from 20.59 to 14.73%. Native starch completely lost their birefringence at 73 °C, while the HMT starch still showed strong birefringence in granule periphery. The HMT starch only lost crystallites at 80 °C (PV2). A crystallite stability hypothesis was developed that G1 was mainly due to the gelatinization of the inner crystalline lamellae of starch granule, and the newly formed G2 was caused by the peripheral ones enhanced by HMT. This work also provided details on the mechanism of HMT and a potential method for the thermal transition study on starch.


Asunto(s)
Almidón/química , Zea mays/química , Gelatina/química , Calor , Microscopía Electrónica de Rastreo , Viscosidad , Difracción de Rayos X
11.
Carbohydr Polym ; 269: 118263, 2021 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-34294296

RESUMEN

Amylose­sodium stearate (SS) complexes (2, 5 and 8%) in heat-moisture treated potato starch (HPS) were evaluated for their physicochemical properties. Based on the DSC thermograms, the amylose - SS complexes were successfully formed with high thermal stability, indicated by a melt temperature (Tpeak) of ≥ 112 °C for type I and ≥125 °C for type II complexes. Addition of 2% SS resulted in a single endothermal peak of the complexes, while 5 and 8% led to the formation of type I and II complexes with much higher enthalpy (ΔH) values. The XRD curve confirmed that the complexes were successfully formed. The pasting temperature increased from 66 °C for native to 91 °C for HPS145 complexed starch with 5% SS. Furthermore, the swelling power could be largely decreased, and the granular structure preserved. In addition, the inclusion complexation with SS on (HPS) succesfully improved the cook stabiliy.

12.
Carbohydr Polym ; 229: 115453, 2020 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-31826416

RESUMEN

This study investigated the acetylation of starch to improve its processability and compatibility with poly(lactic acid). The temperature at the maximum rate of degradation increased by 3.2% for poly(lactic acid) blends containing acetylated starch degree of substitution 2.5 compared to the blend containing neat starch. A biphasic morphology with distinct dispersed phase was predicted and observed experimentally for all blends except the blend containing acetylated starch degree of substitution 3. Acetylated starch induced plasticization and nucleation for all degree of substitution. The blend containing acetylated starch degree of substitution 2.5 had higher tensile strength (26%), and toughness (29%) compared to the blend containing neat starch. The superior mechanical properties of the blend containing acetylated starch degree of substitution 2.5 are attractive for medical implant applications. The continuous microstructure and transparency characteristics of the blend containing acetylated starch degree of substitution 3 are attractive for packaging applications.

13.
Gels ; 6(4)2020 Nov 23.
Artículo en Inglés | MEDLINE | ID: mdl-33238369

RESUMEN

One-pot free-radical polymerization of N-acryloyl glycinamide in the presence of hyaluronic acid as transfer-termination agent led to new copolymers in high yields without any chemical activation of hyaluronic acid before. All the copolymers formed thermoresponsive hydrogels of the Upper Critical Solution Temperature-type in aqueous media. Gel properties and the temperature of the reversible gel ↔ sol transition depended on feed composition and copolymer concentration. Comparison with mixtures of hyaluronic acid-poly(N-acryloyl glycinamide) failed in showing the expected formation of graft copolymers conclusively because poly(N-acryloyl glycinamide) homopolymers are also thermoresponsive. Grafting and formation of comb-like copolymers were proved after degradation of inter-graft hyaluronic acid segments by hyaluronidase. Enzymatic degradation yielded poly(N-acryloyl glycinamide) with sugar residues end groups as shown by NMR. In agreement with the radical transfer mechanism, the molar mass of these released poly(N-acryloyl glycinamide) grafts depended on the feed composition. The higher the proportion of hyaluronic acid in the feed, the lower the molar mass of poly(N-acryloyl glycinamide) grafts was. Whether molar mass can be made low enough to allow kidney filtration remains to be proved in vivo. Last but not least, Prednisolone was used as model drug to show the ability of the new enzymatically degradable hydrogels to sustain progressive delivery for rather long periods of time in vitro.

14.
F1000Res ; 8: 223, 2019.
Artículo en Inglés | MEDLINE | ID: mdl-31031970

RESUMEN

The variation of the color intensity of the chromatophores present in the wings of Schistocerca americana was analyzed by exposing 31 specimens to thermal transitions within the range of 45 - 5 °C.  The adult specimens were collected using a mini-terrarium of dimensions 40x40x30 cm. As a substrate, a layer of soil, stones, and finally a layer of grass were used along with branches of bushes and leaves; hydroponic lettuce, cabbage and the grass were used as food for the specimens. Optical microscopy of the wings of the insects was used for live observation without coverslips or contrasting substances. At 45°C, degradation of color intensity was observed in the chromatophores present in the wings. At 5°C, chromatophores intensify their color to brownish-black. This temperature was the extreme minimum that S. americana could tolerate. We found negative correlation between the temperature and the degree of darkness (R2 = 0.8038). Our results are in accordance with a previously published study in which Phaulacridium vittatum was examined, as the decrease of temperature caused darkening color change in melanin-type chromatophores. The present investigation can be considered as the first initial study of its kind for S. americana, in terms of examining the changes in the color intensity of the chromatophores present in the wings caused by thermal transition under laboratory conditions.


Asunto(s)
Cromatóforos , Insectos , Alas de Animales , Animales , Incidencia
15.
Carbohydr Polym ; 204: 1-8, 2019 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-30366520

RESUMEN

Starch is an important class of macromolecules for human nutrition. However, its rapid digestibility leads to a high amount of glucose released into the blood and contributes to a high risk of obesity and type II diabetes. For these reasons, Heat-moisture treatment (HMT) of the starch was applied prior to complexation with linoleic acid to obtain a desired physicochemical properties while preserving its granular structure. The thermal properties, analyzed by DSC, implied that the HMT enhanced the formation of amylose-linoleic acid complexes, particularly when the complexation was succeeded at 70 °C. The viscosity behavior studied by RVA demonstrated a higher pasting temperature and lower peak viscosity due to less swelling. The granule-like structure remained after complexation at 70 °C for 30 min and followed by RVA to 85 °C. The combination of the HMT and linoleic acid addition improved the stability of the starch granules towards heating and shearing.

16.
Polymers (Basel) ; 10(4)2018 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-30966427

RESUMEN

The present work deals with the synthesis of micro-structured biomaterials based on chitosan (CTS) for their applications as biocompatible carriers of drugs and bioactive compounds. Twelve dispersions were prepared by means of functional cross-linking with tricarballylic acid (TCA); they were characterized by Fourier transform infrared spectroscopy (FT-IR), modulated temperature differential scanning calorimetry (MTDSC) and scanning electron microscopy (SEM), and their rheological properties were studied. To the best of the authors' knowledge, no study has been carried out on the influence of CTS concentration, degree of cross-linking and drug loading on chitosan hydrogels for drug delivery systems (DDS) and is investigated herein for the first time. The influence of dispersion composition (polymer concentration and degree of cross-linking) revealed to exert a marked impact on its rheological properties, going from liquid-like to viscoelastic gels. The release profiles of a model drug, diclofenac sodium (DCNa), as well as their relationships with polymer concentration, drug loading and degree of cross-linking were evaluated. Similar to the findings on rheological properties, a wide range of release profiles was encountered. These formulations were found to display a well-controlled drug release strongly dependent on the formulation composition. Cumulative drug release under physiological conditions for 96 h ranged from 8% to 67%. For comparative purpose, Voltaren emulgel® from Novartis Pharmaceuticals was also investigated and the latter was the formulation with the highest cumulative drug release (85%). Some formulations showed similar spreadability values to the commercial hydrogel. The comparative study of three batches confirmed the reproducibility of the method, leading to systems particularly suitable for their use as drug carriers.

17.
ACS Appl Mater Interfaces ; 9(45): 39717-39727, 2017 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-29068220

RESUMEN

Three-dimensional (3D) macroporous graphene foam based multifunctional epoxy composites are developed in this study. Facile dip-coating and mold-casting techniques are employed to engineer microstructures with tailorable thermal, mechanical, and electrical properties. These processing techniques allow capillarity-induced equilibrium filling of graphene foam branches, creating epoxy/graphene interfaces with minimal separation. Addition of 2 wt % graphene foam enhances the glass transition temperature of epoxy from 106 to 162 °C, improving the thermal stability of the polymer composite. Graphene foam aids in load-bearing, increasing the ultimate tensile strength by 12% by merely 0.13 wt % graphene foam in an epoxy matrix. Digital image correlation (DIC) analysis revealed that the graphene foam cells restrict and confine the deformation of the polymer matrix, thereby enhancing the load-bearing capability of the composite. Addition of 0.6 wt % graphene foam also enhances the flexural strength of the pure epoxy by 10%. A 3D network of graphene branches is found to suppress and deflect the cracks, arresting mechanical failure. Dynamic mechanical analysis (DMA) of the composites demonstrated their vibration damping capability, as the loss tangent (tan δ) jumps from 0.1 for the pure epoxy to 0.24 for ∼2 wt % graphene foam-epoxy composite. Graphene foam branches also provide seamless pathways for electron transfer, which induces electrical conductivity exceeding 450 S/m in an otherwise insulator epoxy matrix. The epoxy-graphene foam composite exhibits a gauge factor as high as 4.1, which is twice the typical gauge factor for the most common metals. Simultaneous improvement in thermal, mechanical, and electrical properties of epoxy due to 3D graphene foam makes epoxy-graphene foam composite a promising lightweight and multifunctional material for aiding load-bearing, electrical transport, and motion sensing in aerospace, automotive, robotics, and smart device structures.

18.
Carbohydr Polym ; 151: 198-205, 2016 Oct 20.
Artículo en Inglés | MEDLINE | ID: mdl-27474558

RESUMEN

Apios americana is a wild legume-bearing plant with edible tubers. Domestication of Apios is in progress because of the superior nutritional value and health benefits of the tuber. Objectives of this study were to: (1) characterize physicochemical properties of the Apios tuber starch; and (2) understand differences in starch structures and properties between the mother (seed) and child (progeny) tubers and the mechanism of starch development. Granules of the Apios tuber starch displayed ellipsoidal, rod, or kidney shape with diameter ranges of 1-30µm. The mother tuber starches displayed greater percentage crystallinity, larger gelatinization enthalpy-changes, longer branch-chain lengths of amylopectin, and lower pasting viscosity than their counterpart child tuber starches. The mother tuber starch of Apios 2127 displayed distinct two peaks of gelatinization, which were attributed to starch granules located at different regions of the tuber having different structures and properties. The mother tuber displayed more active starch biosynthesis in the periphery than in the center of the tuber.


Asunto(s)
Fabaceae , Tubérculos de la Planta , Almidón/química , Amilosa/análisis , Fabaceae/metabolismo , Tubérculos de la Planta/metabolismo , Almidón/biosíntesis , Viscosidad
19.
Appl Ergon ; 54: 169-76, 2016 May.
Artículo en Inglés | MEDLINE | ID: mdl-26851476

RESUMEN

The study was done to identify affective and sensory responses observed as a result of hysteresis effects in transient thermal conditions consisting of warm-neutral and neutral - warm performed in a quasi-experiment setting. Air-conditioned building interiors in hot-humid areas have resulted in thermal discomfort and health risks for people moving into and out of buildings. Reports have shown that the instantaneous change in air temperature can cause abrupt thermoregulation responses. Thermal sensation vote (TSV) and thermal comfort vote (TCV) assessments as a consequence of moving through spaces with distinct thermal conditions were conducted in an existing single-story office in a hot-humid microclimate, maintained at an air temperature 24 °C (± 0.5), relative humidity 51% (± 7), air velocity 0.5 m/s (± 0.5), and mean radiant temperature (MRT) 26.6 °C (± 1.2). The measured office is connected to a veranda that showed the following semi-outdoor temperatures: air temperature 35 °C (± 2.1), relative humidity 43% (± 7), air velocity 0.4 m/s (± 0.4), and MRT 36.4 °C (± 2.9). Subjective assessments from 36 college-aged participants consisting of thermal sensations, preferences and comfort votes were correlated against a steady state predicted mean vote (PMV) model. Local skin temperatures on the forehead and dorsal left hand were included to observe physiological responses due to thermal transition. TSV for veranda-office transition showed that no significant means difference with TSV office-veranda transition were found. However, TCV collected from warm-neutral (-0.24, ± 1.2) and neutral-warm (-0.72, ± 1.3) conditions revealed statistically significant mean differences (p < 0.05). Sensory and affective responses as a consequence of thermal transition after travel from warm-neutral-warm conditions did not replicate the hysteresis effects of brief, slightly cool, thermal sensations found in previous laboratory experiments. These findings also indicate that PMV is an acceptable alternative to predict thermal sensation immediately after a down-step thermal transition (≤ 1 min exposure duration) for people living in a hot-humid climate country.


Asunto(s)
Aire Acondicionado/efectos adversos , Microclima , Sensación Térmica , Clima Tropical , Lugar de Trabajo/psicología , Adulto , Aire Acondicionado/métodos , Movimientos del Aire , Regulación de la Temperatura Corporal/fisiología , Emociones , Femenino , Calor , Humanos , Humedad , Masculino , Ensayos Clínicos Controlados no Aleatorios como Asunto , Temperatura Cutánea , Encuestas y Cuestionarios , Adulto Joven
20.
MAbs ; 7(1): 212-30, 2015.
Artículo en Inglés | MEDLINE | ID: mdl-25559441

RESUMEN

High viscosity of monoclonal antibody formulations at concentrations ≥100 mg/mL can impede their development as products suitable for subcutaneous delivery. The effects of hydrophobic and electrostatic intermolecular interactions on the solution behavior of MAB 1, which becomes unacceptably viscous at high concentrations, was studied by testing 5 single point mutants. The mutations were designed to reduce viscosity by disrupting either an aggregation prone region (APR), which also participates in 2 hydrophobic surface patches, or a negatively charged surface patch in the variable region. The disruption of an APR that lies at the interface of light and heavy chain variable domains, VH and VL, via L45K mutation destabilized MAB 1 and abolished antigen binding. However, mutation at the preceding residue (V44K), which also lies in the same APR, increased apparent solubility and reduced viscosity of MAB 1 without sacrificing antigen binding or thermal stability. Neutralizing the negatively charged surface patch (E59Y) also increased apparent solubility and reduced viscosity of MAB 1, but charge reversal at the same position (E59K/R) caused destabilization, decreased solubility and led to difficulties in sample manipulation that precluded their viscosity measurements at high concentrations. Both V44K and E59Y mutations showed similar increase in apparent solubility. However, the viscosity profile of E59Y was considerably better than that of the V44K, providing evidence that inter-molecular interactions in MAB 1 are electrostatically driven. In conclusion, neutralizing negatively charged surface patches may be more beneficial toward reducing viscosity of highly concentrated antibody solutions than charge reversal or aggregation prone motif disruption.


Asunto(s)
Sustitución de Aminoácidos , Anticuerpos Monoclonales/química , Anticuerpos Monoclonales/genética , Mutación Puntual , Humanos , Interacciones Hidrofóbicas e Hidrofílicas , Solubilidad , Electricidad Estática , Viscosidad
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