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1.
Adv Mater ; 35(14): e2211648, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36634260

RESUMEN

Skeletal muscles are natural motors executing sophisticated work through precise control of linear contraction. Although various liquid crystal polymers based artificial muscles have been designed, the mechanism based on mainly the order-disorder transition usually leads to discrete shape morphing, leaving arbitrary and precise deformation a huge challenge. Here, one novel photoresponsive hemiphasmidic side-chain liquid crystal polymer with a unique "breathing" columnar phase that enables continuous morphing is presented. Due to confinement inside the supramolecular columnar assembly, the cooperative movements of side-chains and backbones generate a significant negative thermal expansion and lead to temperature-controllable muscle-like elongation/contraction in the oriented polymer strip. The irreversible isomerization of the photoresponsive mesogens results in the synergistic phototunable bending and high-contrast fluorescence change. Based on the orthogonal responses to heat and light, controllable arm-like bending motions of this material, which is applicable in constructing advanced artificial muscles or intelligent soft robotics, are further demonstrated.

2.
ACS Nano ; 15(12): 19418-19429, 2021 Dec 28.
Artículo en Inglés | MEDLINE | ID: mdl-34874720

RESUMEN

We demonstrate bioenabled crack-free chiral nematic films prepared via a unidirectional flow of cellulose nanocrystals (CNCs) in the capillary confinement. To facilitate the uniform long-range nanocrystal organization during drying, we utilized tunicate-inspired hydrogen-bonding-rich 3,4,5-trihydroxyphenethylamine hydrochloride (TOPA) for physical cross-linking of nanocrystals with enhanced hydrogen bonding and polyethylene glycol (PEG) as a relaxer of internal stresses in the vicinity of the capillary surface. The CNC/TOPA/PEG film is organized as a left-handed chiral structure parallel to flat walls, and the inner volume of the films displayed transitional herringbone organization across the interfacial region. The resulting thin films also exhibit high mechanical performance compared to brittle films with multiple cracks commonly observed for capillary-formed pure CNC films. The chiral nematic ordering of modified TOPA-PEG-CNC material propagates through the entire thickness of robust monolithic films and across centimeter-sized surface areas, facilitating consistent, vivid iridescence, and enhanced circular polarization. The best performance that prevents the cracks was achieved for a CNC/TOPA/PEG film with a minimal, 3% amount of TOPA. Overall, we suggest that intercalation of small highly adhesive molecules to cellulose nanocrystal-polymer matrices can facilitate uniform flow of liquid crystal phase and drying inside the capillary, resulting in improvement of the ultimate tensile strength and toughness (77% and 100% increase, respectively) with controlled uniform optical reflection and enhanced circular polarization unachievable during regular drying conditions.

3.
Small ; 17(26): e2008097, 2021 07.
Artículo en Inglés | MEDLINE | ID: mdl-34081393

RESUMEN

Biomacromolecules are likely to undergo self-assembly and show specific collective behavior concentrated in the medium. Although the assembly procedures have been studied for unraveling their mysteries, there are few cases to directly demonstrate the collective behavior and phase transition process in dynamic systems. In the contribution, the drying process of M13 droplet is investigated, and can be successfully simulated by a doctor blade coating method. The morphologies in the deposited film are measured by atomic force microscopy and the liquid crystal phase development is captured in real time using polarized optical microscope. Collective behaviors near the contact line are characterized by the shape of meniscus curve and particle movement velocity. With considering rheological properties and flow, the resultant chiral film is used to align gold nanorods, and this approach can suggest a way to use M13 bacteriophage as a scaffold for the multi-functional chiral structures.


Asunto(s)
Cristales Líquidos , Nanotubos , Bacteriófago M13 , Oro , Microscopía de Fuerza Atómica
4.
Small ; 17(30): e2007306, 2021 07.
Artículo en Inglés | MEDLINE | ID: mdl-34047461

RESUMEN

As a nanoscale renewable resource derived from lignocellulosic materials, cellulose nanocrystals (CNCs) have the features of high purity, high crystallinity, high aspect ratio, high Young's modulus, and large specific surface area. The most interesting trait is that they can form the entire films with bright structural colors through the evaporation-induced self-assembly (EISA) process under certain conditions. Structural color originates from micro-nano structure of CNCs matrixes via the interaction of nanoparticles with light, rather than the absorption and reflection of light from the pigment. CNCs are the new generation of photonic liquid crystal materials of choice due to their simple and convenient preparation processes, environmentally friendly fabrication approaches, and intrinsic chiral nematic structure. Therefore, understanding the forming mechanism of CNCs in nanoarchitectonics is crucial to multiple fields of physics, chemistry, materials science, and engineering application. Herein, a timely summary of the chiral photonic liquid crystal films derived from CNCs is systematically presented. The relationship of CNC, structural color, chiral nematic structure, film performance, and applications of chiral photonic liquid crystal films is discussed. The review article also summarizes the most recent achievements in the field of CNCs-based photonic functional materials along with the faced challenges.


Asunto(s)
Cristales Líquidos , Nanopartículas , Nanoestructuras , Celulosa , Óptica y Fotónica
5.
J Colloid Interface Sci ; 601: 98-105, 2021 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-34058556

RESUMEN

HYPOTHESIS: Bottom-up synthesis of cubosomes is more energetically favourable than top-down approaches. However, bottom-up methods often rely on organic solvents such as ethanol as diluents, and lead to concurrent formation of liposomes. We propose using non-toxic diluents such as honey, glycerol and lactic acid for bottom-up cubosome synthesis. EXPERIMENTS: Cubosomes were prepared using solutions of phytantriol in a range of diluents including choline chloride-glycerol, honey, lactic acid, glycerol, and ethanol. These solutions were added dropwise to water containing the stabiliser, poloxamer 407, following an established method of cubosome synthesis. The resulting structures were characterised using small-angle X-ray scattering, DLS and cryo-TEM. FINDINGS: Cubosomes were successfully formed using a range of non-toxic diluents. This demonstrates that harmful organic solvents like ethanol are not required, and that the diluents need not be hydrotropes. Furthermore, unlike ethanol, these other diluents allowed formation of cubosomes without concurrent formation of liposomes. Given the huge potential for cubosomes in drug delivery, this new method offers a potentially useful low-cost, low-toxicity synthesis option.


Asunto(s)
Sistemas de Liberación de Medicamentos , Poloxámero , Excipientes , Liposomas , Solventes
6.
Nano Lett ; 18(11): 6770-6777, 2018 11 14.
Artículo en Inglés | MEDLINE | ID: mdl-30351961

RESUMEN

We showed large area uniformly aligned chiral photonic bioderived films from a liquid crystal phase formed by a cellulose nanocrystal (CNC) suspension placed in a thin capillary. As a result of the spatial confinement of the drying process, the interface between coexisting isotropic and chiral phases aligns perpendicular to the long axis of the capillary. This orientation facilitates a fast homogeneous growth of chiral pseudolayers parallel to the interface. Overall, the formation of organized solids takes hours vs weeks in contrast to the slow and heterogeneous process of drying from the traditional dish-cast approach. The saturation of water vapor in one end of the capillary causes anisotropic drying and promotes unidirectional propagation of the anisotropic phase in large regions that results in chiral CNC solid films with a uniformly oriented layered morphology. Corresponding ordering processes were monitored in situ at a nanoscale, mesoscale, and microscopic scale with complementary scattering and microscopic techniques. The resulting films show high orientation order at a multilength scale over large regions and preserved chiral handedness causing a narrower optical reflectance band and uniform birefringence over macroscopic regions in contrast to traditional dish-cast CNC films and those assembled in a magnetic field and on porous substrates. These thin films with a controllable and well-identified uniform morphology, structural colors, and handedness open up interesting possibilities for broad applications in bioderived photonic nanomaterials.

7.
Materials (Basel) ; 10(11)2017 Nov 09.
Artículo en Inglés | MEDLINE | ID: mdl-29120371

RESUMEN

We have previously reported the first realization of an orthogonal ferroelectric bent-core SmAPF phase by directed design in mesogens with a single tricarbosilane-terminated alkoxy tail. Given the potentially useful electrooptic properties of this phase, including analog phase-only electrooptic index modulation with optical latching, we have been exploring its "structure space", searching for novel SmAPF mesogens. Here, we report two classes of these-the first designed to optimize the dynamic range of the index modulation in parallel-aligned cells by lowering the bend angle of the rigid core, and the second expanding the structure space of the phase by replacing the tricarbosilane-terminated alkyl tail with a polyfluorinated polyethylene glycol oligomer.

8.
Sci Adv ; 3(2): e1602102, 2017 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-28246642

RESUMEN

A lamellar liquid crystal (LC) phase of certain bent-core mesogenic molecules can be grown in a manner that generates a single chiral helical nanofilament in each of the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. By introducing guest molecules into the resulting composite chiral nanochannels, we explore the structures and functionality of the ordered guest/host LC complex, verifying the smectic-like positional order of the fluidic nematic LC phase, which is obtained by the combination of the LC organization and the nanoporous AAO superstructure. The guest nematic LC 4'-n-pentyl-4-cyanobiphenyl is found to form a distinctive fluid layered ordered LC complex at the nanofilament/guest interface with the host 1,3-phenylene bis[4-(4-nonyloxyphenyliminomethyl)benzoate], where this interface contacts the AAO cylinder wall. Filament growth form is strongly influenced by mixture parameters and pore dimensions.

9.
Eur J Pharm Sci ; 101: 31-42, 2017 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-28137471

RESUMEN

From the last couple of decades, lyotropic liquid crystals have garnered enormous attentions in medical and pharmaceutical sciences. Non-toxic, chemically stable, and biocompatible properties of these liquid crystal systems are contributing to their applications for drug delivery. Among a large variety of liquid crystal phases, inverse bicontinuous cubic and inverse hexagonal mesophases have been extensively investigated for their ability to encapsulate and controlled release of bioactive molecules of various sizes and polarity. The concept of changing the drug release rate in situ by simply changing the mesophase structure is much more fascinating. The encapsulation of bioactive compounds in mesophase systems of desirable features in sub-micron sized particles such as hexosomes and cubosomes, at ambient and high temperature is bringing innovation in the development of new drug applications. This review article outlines unique structural features of cubosomes and hexosomes, their methods of productions, factors affecting their formations and their potential utilization as smart nano-carriers for biopharmaceuticals in drug delivery applications.


Asunto(s)
Portadores de Fármacos/química , Alcoholes Grasos/química , Nanopartículas/química , Sistemas de Liberación de Medicamentos/métodos , Liberación de Fármacos , Cristales Líquidos/química , Tamaño de la Partícula
10.
Mater Sci Eng C Mater Biol Appl ; 58: 977-85, 2016 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-26478394

RESUMEN

To duplicate collagen's in vivo liquid crystalline (LC) phase and investigate the relationship between the morphology of LC collagen and osteoblast behavior, a self-assembly method was introduced for preparing collagen films with a stabilized LC phase. The LC texture and topological structure of the films before and after stabilization were observed with polarizing optical microscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM). The relationship between the collagen films and osteoblast behavior was studied with the 3-(4,5)-dimethylthiahiazo(-z-y1)-3,5-di-phenytetrazoliumromide method, proliferation index detection, alkaline phosphatase measurements, osteocalcin assay, inverted microscopy, SEM observation, AFM observation, and cytoskeleton fluorescence staining. The results showed that the LC collagen film had continuously twisting orientations in the cholesteric phase with a typical series of arced patterns. The collagen fibers assembled in a well-organized orientation in the LC film. Compared to the non-LC film, the LC collagen film can promote cell proliferation, and increase ALP and osteocalcin expression, revealing a contact guide effect on osteoblasts.


Asunto(s)
Colágeno Tipo I/química , Cristales Líquidos/química , Osteoblastos/citología , Fosfatasa Alcalina/metabolismo , Animales , Adhesión Celular , Proliferación Celular , Células Cultivadas , Citoesqueleto/química , Citoesqueleto/metabolismo , Puntos de Control de la Fase G1 del Ciclo Celular/efectos de los fármacos , Microscopía de Fuerza Atómica , Microscopía Electrónica de Rastreo , Osteoblastos/metabolismo , Osteocalcina/metabolismo , Ratas , Ratas Sprague-Dawley
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