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1.
Adv Mater ; : e2104634, 2021 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-34541730

RESUMO

Metal-polymer composites (MPCs) with combined properties of metals and polymers have achieved much industrial success. However, metals in MPCs are thought to be ordinary and invariable electrically conductive fillers in supportive polymers to show limited use in modern technologies. This work that is disclosed here, for the first time, introduces stimuli-driven transition from biphasic to monophasic state of liquid metal into polymer science to form dynamic soft conductors from the binary metal-polymer composites. The binary metal that exhibits temperature-driven reversible transition between solid and liquid states via a biphasic state is fabricated. A conducting stretchable polymer composite is developed using the judiciously chosen biphasic binary metal that undergoes conductor to insulator transition upon stretching. Insulating stretched films become conducting upon heating. A "tube" model elegantly describes such distinctive deformation/temperature-dependent behaviors. Moreover, the conducting polymer composite shows decrease in its resistance upon increasing the sample temperature. The resistance can be tuned from 1 to 108  Ω depending on the state of binary metal in the phase diagram. This work would build the intimate and interesting connection between metal phases and polymer science toward next-generation soft conductors and beyond.

2.
Adv Sci (Weinh) ; : e2102674, 2021 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-34569166

RESUMO

With the advantage of reversible shape-morphing between two different permanent shapes under external stimuli, the two-way shape-memory aerogel is expected to become a preferred aerogel for developing practical applications in actuators, sensors, robotics, and more. Herein, the first two-way shape-memory liquid crystal elastomer (LCE)-based aerogel is prepared by an orthogonal heat and light curing strategy coupled with an intermediate mechanical stretching step. The differential scanning calorimetry, temperature-varied wide-angle X-ray scattering, and polarizing optical microscope results indicate that the aerogel possesses a liquid crystal phase and the insider mesogens are well-oriented along the stretching direction. In addition to having superior compressibility and excellent shape stability, this LCE-based aerogel can perform a reversible shape deformation during the heating/cooling cycles with a shrinkage ratio of 37%. The work, that is disclosed here, realizes a truly two-way shape-memory behavior rather than the one-way shape deformation of traditional polymer aerogel materials, and may promote potential applications of this novel LCE-based aerogel material in control devices, soft actuators, and beyond.

3.
Nat Commun ; 12(1): 4993, 2021 08 17.
Artigo em Inglês | MEDLINE | ID: mdl-34404798

RESUMO

Dissipative self-assembly, which requires a continuous supply of fuel to maintain the assembled states far from equilibrium, is the foundation of biological systems. Among a variety of fuels, light, the original fuel of natural dissipative self-assembly, is fundamentally important but remains a challenge to introduce into artificial dissipative self-assemblies. Here, we report an artificial dissipative self-assembly system that is constructed from light-induced amphiphiles. Such dissipative supramolecular assembly is easily performed using protonated sulfonato-merocyanine and chitosan based molecular and macromolecular components in water. Light irradiation induces the assembly of supramolecular nanoparticles, which spontaneously disassemble in the dark due to thermal back relaxation of the molecular switch. Owing to the presence of light-induced amphiphiles and the thermal dissociation mechanism, the lifetimes of these transient supramolecular nanoparticles are highly sensitive to temperature and light power and range from several minutes to hours. By incorporating various fluorophores into transient supramolecular nanoparticles, the processes of aggregation-induced emission and aggregation-caused quenching, along with periodic variations in fluorescent color over time, have been demonstrated. Transient supramolecular assemblies, which act as fluorescence modulators, can also function in human hepatocellular cancer cells.


Assuntos
Corantes Fluorescentes/química , Nanopartículas/química , Água/química , Fluorescência , Células Hep G2 , Humanos , Cinética , Substâncias Macromoleculares , Temperatura
4.
Artigo em Inglês | MEDLINE | ID: mdl-33977661

RESUMO

Based on liquid crystal elastomer (LCE) materials, hierarchically structured soft actuators can meet some requirements for "human-friendly" working mode and execute complex tasks with intelligent adaptation to environmental changes. However, few researchers have paid much attention to the preparation methods of multicomponent/hierarchical LCE actuators. In this communication, we demonstrate the successful integration of an exchangeable diselenide chain extender for the preparation of dynamic LCEs, which could be reprogrammed on heating or under visible light illumination. Moreover, the rearrangeable polydiselenide networks could be applied to develop the self-welding technology toward fabricating hierarchically structured LCE actuators with sophisticated deformability without using any auxiliary reagent (adhesive, tape, catalysts or initiator) during the assembling process.

5.
Nat Commun ; 12(1): 2339, 2021 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-33879783

RESUMO

Developing organic photoluminescent materials with high emission efficiencies in the solid state under a water atmosphere is important for practical applications. Herein, we report the formation of both intra- and intermolecular hydrogen bonds in three tautomerizable Schiff-base molecules which comprise active hydrogen atoms that act as proton donors and acceptors, simultaneously hindering emission properties. The intercalation of water molecules into their crystal lattices leads to structural rearrangement and organic hydrate luminogen formation in the crystalline phase, triggering significantly enhanced fluorescence emission. By suppressing hydrogen atom shuttling between two nitrogen atoms in the benzimidazole ring, water molecules act as hydrogen bond donors to alter the electronic transition of the molecular keto form from nπ* to lower-energy ππ* in the excited state, leading to enhancing emission from the keto form. Furthermore, the keto-state emission can be enhanced using deuterium oxide (D2O) owing to isotope effects, providing a new opportunity for detecting and quantifying D2O.

6.
Langmuir ; 2021 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-33775094

RESUMO

The quest for interesting properties and phenomena in liquid crystals toward their employment in nondisplay application is an intense and vibrant endeavor. Remarkable progress has recently been achieved with regard to liquid crystals in curved confined geometries, typically represented as enclosed spherical geometries and cylindrical geometries with an infinitely extended axial-symmetrical space. Liquid-crystal emulsion droplets and fibers are intriguing examples from these fields and have attracted considerable attention. It is especially noteworthy that the rapid development of microfluidics brings about new capabilities to generate complex soft microstructures composed of both thermotropic and lyotropic liquid crystals. This review attempts to outline the recent developments related to the liquid crystals in curved confined geometries by focusing on microfluidics-mediated approaches. We highlight a wealth of novel photonic applications and beyond and also offer perspectives on the challenges, opportunities, and new directions for future development in this emerging research area.

7.
Angew Chem Int Ed Engl ; 60(20): 11247-11251, 2021 05 10.
Artigo em Inglês | MEDLINE | ID: mdl-33655581

RESUMO

Bioinspired smart materials with synergistic allochroic luminescence and complex deformation are expected to play an important role in many areas of science and technology. However, it is still challenging to fabricate such soft actuators with high programmability that can be manipulated in situ with high spatial resolution. Herein, we have incorporated terminally functionalized aggregation-induced emission active tetraphenylethene derivative and photochromic spiropyran moieties into the networks of liquid crystal elastomers through covalent bonding to obtain the synergistic photochromic luminescence and programmable soft actuators. Bio-mimic functions and light-induced auxetic metamaterial-like devices were shown to be feasible based on the combination of assembly and origami-programming strategy. These bioinspired devices with synergistic photochromic luminescence and complex photodeformation abilities provide an elegant strategy to design multi-functional liquid crystal actuators.

8.
Angew Chem Int Ed Engl ; 60(7): 3390-3396, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-33259120

RESUMO

Herein, we report near-infrared (NIR) light-driven shape-morphing of programmable MXene-containing anisotropic hydrogel actuators that are fabricated through in situ free-radical copolymerization of a judiciously designed MXene nanomonomer with thermosensitive hydrogel network. A low electric field (few V mm-1 ) was found to enable a spatial distribution of MXene nanosheets and hence introduce anisotropy into the hydrogel network. Programmable anisotropic hydrogel actuators were developed by controlling ITO electrode pattern, direct-current (DC) electric field direction and mask-assisted photopolymerization. As a proof-of-concept, we demonstrate NIR light-driven shape morphing of the MXene-containing anisotropic hydrogel into various shapes and devise a four-arm soft gripper that can perform distinct photomechanical functions such as grasping, lifting/lowering down and releasing an object upon sequential NIR light exposure.

9.
ACS Appl Mater Interfaces ; 12(49): 55215-55222, 2020 Dec 09.
Artigo em Inglês | MEDLINE | ID: mdl-33237715

RESUMO

Self-organized functional soft materials, enabled by specific chemical architectures, are currently attracting tremendous attention because of their stimuli-responsive attributes and applications in advanced technological devices. A novel axially chiral molecular switch containing two azo linkages and six terminal alkyl chains on two elongated rod-shaped wings, that exhibits superior solubility, high helical twisting power, and reversible photoisomerization in an achiral liquid crystal host, is synthesized and utilized in the development of a photoresponsive, self-organized helical superstructure, that is, cholesteric liquid crystal (CLC). The planar CLC adopts a standing helix (SH) configuration because of surface alignment layers on the substrates. This SH can be transitioned to a lying helix configuration, enabling tunable diffraction gratings under the application of electric field. Adjustment of the initial pitch of the planar CLC by photoirradiation yields the diffraction gratings with stripes either parallel or perpendicular to the rubbing direction upon the application of an appropriate electric field. Tunable beam steering along orthogonal directions has been demonstrated. Such tunable stimuli-responsive soft materials fabricated with artificial chiral switches show great potential in optics, photonics, and beyond.

10.
Angew Chem Int Ed Engl ; 59(26): 10493-10497, 2020 06 22.
Artigo em Inglês | MEDLINE | ID: mdl-32196893

RESUMO

Light-harvesting systems are an important way for capturing, transferring and utilizing light energy. It remains a key challenge to develop highly efficient artificial light-harvesting systems. Herein, we report a supramolecular co-assembly based on lower-rim dodecyl-modified sulfonatocalix[4]arene (SC4AD) and naphthyl-1,8-diphenyl pyridinium derivative (NPS) as a light-harvesting platform. NPS as a donor shows significant aggregation induced emission enhancement (AIEE) after assembling with SC4AD. Upon introduction of Nile blue (NiB) as an acceptor into the NPS-SC4AD co-assembly, the light-harvesting system becomes near-infrared (NIR) emissive (675 nm). Importantly, the NIR emitting NPS-SC4AD-NiB system exhibits an ultrahigh antenna effect (33.1) at a high donor/acceptor ratio (250:1). By co-staining PC-3 cells with a Golgi staining reagent, NBD C6 -ceramide, NIR imaging in the Golgi apparatus has been demonstrated using these NIR emissive nanoparticles.


Assuntos
Calixarenos/química , Corantes Fluorescentes/química , Complexo de Golgi/metabolismo , Compostos de Piridínio/química , Calixarenos/efeitos da radiação , Calixarenos/toxicidade , Transferência Ressonante de Energia de Fluorescência , Corantes Fluorescentes/efeitos da radiação , Corantes Fluorescentes/toxicidade , Humanos , Raios Infravermelhos , Microscopia Confocal , Microscopia de Fluorescência , Nanopartículas/química , Nanopartículas/efeitos da radiação , Nanopartículas/toxicidade , Oxazinas/química , Oxazinas/efeitos da radiação , Oxazinas/toxicidade , Células PC-3 , Compostos de Piridínio/efeitos da radiação , Compostos de Piridínio/toxicidade
11.
Angew Chem Int Ed Engl ; 59(7): 2684-2687, 2020 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-31802595

RESUMO

Visible-light-driven molecular switches endowing reversible modulation of the functionalities of self-organized soft materials are currently highly sought after for fundamental scientific studies and technological applications. Reported herein are the design and synthesis of two novel halogen bond donor based chiral molecular switches that exhibit reversible photoisomerization upon exposure to visible light of different wavelengths. These chiral molecular switches induce photoresponsive helical superstructures, that is, cholesteric liquid crystals, when doped into the commercially available room-temperature achiral liquid crystal host 5CB, which also acts as a halogen-bond acceptor. The induced helical superstructure containing the molecular switch with terminal iodo atoms exhibits visible-light-driven reversible unwinding, that is, a cholesteric-nematic phase transition. Interestingly, the molecular switch with terminal bromo atoms confers reversible handedness inversion to the helical superstructure upon irradiation with visible light of different wavelengths. This visible-light-driven, reversible handedness inversion, enabled by a halogen bond donor molecular switch, is unprecedented.

12.
Sci Adv ; 5(10): eaax9501, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31620560

RESUMO

Dynamic modulation of soft helix in terms of the molecular organization, handedness, and pitch length could result in a sophisticated control over its functions, opening numerous possibilities toward the exploration of previously unidentified applications. Here, we report a dynamic and reversible transformation of a soft helical superstructure among the helicoidal (molecules orthogonal to helical axis), heliconical (molecules oblique to the helical axis, i.e., oblique helicoidal), and their inverse helices, together with a tunability on the helical pitch, by combining electrical and optical manipulations. This multistate transformation depends on a matching of the temperature, the strength of external stimuli, and the bend and twist elastic effects of the system. A laser emission with tunable wavelength and polarization, and prescribed micropatterns formed by any aforementioned architectures were achieved.

13.
Angew Chem Int Ed Engl ; 58(45): 16052-16056, 2019 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-31487106

RESUMO

Reported here is the first example of a 1,2-dithienyldicyanoethene-based visible-light-driven chiral fluorescent molecular switch that exhibits reversible trans to cis photoisomerization. The trans form in solution almost completely transforms into the cis form, accompanied by a 10-fold decrease in its fluorescence intensity within 60 seconds when exposed to green light (520 nm). The reverse isomerization proceeds upon irradiation with blue light (405 nm). When doped into commercially available achiral liquid crystal hosts, this molecular switch efficiently induces luminescent helical superstructures, that is, a cholesteric phase. The intensity of the circularly polarized fluorescence as well as the selective reflection wavelength of the induced cholesteric phases can be reversibly tuned using visible light of two different wavelengths. Optically rewritable photonic devices using cholesteric films containing this molecular switch are described.

14.
Adv Mater ; 31(39): e1902958, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31402517

RESUMO

Light-induced phenomena occurring in nature and in synthetic materials are fascinating and have been exploited for technological applications. Here visible-light-induced formation of a helical superstructure is reported, i.e., a cholesteric liquid crystal phase, in orientationally ordered fluids, i.e., nematic liquid crystals, enabled by a visible-light-driven chiral molecular switch. The cyclic-azobenzene-based chiral molecular switch exhibits reversible photoisomerization in response to visible light of different wavelengths due to the band separation of n-π* transitions of its trans- and cis-isomers. Green light (530 nm) drives the trans-to-cis photoisomerization whereas the cis-to-trans isomerization process of the chiral molecular switch can be caused by blue light (440 nm). It is observed that the helical twisting power of this chiral molecular switch increases upon irradiation with green light, which enables reversible induction of helical superstructure in nematic liquid crystals containing a very small quantity of the molecular switch. The occurrence of the light-induced helical superstructure enables the formation of diffraction gratings in cholesteric films.

15.
Nat Commun ; 10(1): 2518, 2019 06 07.
Artigo em Inglês | MEDLINE | ID: mdl-31175286

RESUMO

Active planar optical devices that can dynamically manipulate light are highly sought after in modern optics and nanophotonics. The geometric phase derived from the photonic spin-orbit interaction provides an integrated strategy. Corresponding elements usually suffer from static functions. Here, we introduce an inhomogeneously self-organized anisotropic medium featured by photo-invertible chiral superstructure to realize geometric phase elements with continuously tunable working spectrum and light-flipped phase profile. Via preprograming the alignment of a cholesteric liquid crystal mixed with a photo-responsive chiral dopant, we demonstrate light-activated deflector, lens, Airy beam and optical vortex generators. Their polychromatic working bands are reversibly tuned in an ultra-broadband over 1000 nm covering green to telecomm region. The chirality inversion triggers facile switching of functionalities, such as beam steering, focusing/defocusing and spin-to-orbital angular momentum conversion. This work offers a platform for advanced adaptive and multifunctional flat optics with merits of high compactness, low loss and broad bandwidth.

16.
J Am Chem Soc ; 141(20): 8078-8082, 2019 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-31050406

RESUMO

Development of light-driven functional materials capable of displaying reversible properties is currently a vibrant frontier from both scientific and technological points of view. Here a new visible-light-driven chiral molecular switch is synthesized and characterized. To the best of our knowledge, this is the first example of a chiral molecular switch in which the visible-light-driven azobenzene motif is directly linked to an axially chiral scaffold through a C-C bond. The chiral molecular switch exhibits trans-to- cis photoisomerization upon 530 nm irradiation and cis-to- trans isomerization upon 450 nm irradiation. The switch can thus be photoisomerized in both directions using visible light of different wavelengths, a promising attribute for device applications. It was found that this relatively rigid molecular switch exhibited a high helical twisting power (HTP) in liquid crystal hosts and a large change of HTP value upon photoisomerization. We achieved dynamic reflection tuning across the visible spectrum through incorporation into a self-organized helical superstructure, i.e., a cholesteric liquid crystal. We also demonstrated patterned photodisplays reflecting red, green, and blue circularly polarized light using these cholesteric films. Phototunable color displays were fabricated by selective light irradiation where the information can be reversibly hidden by applying an electric field and restored by applying either a mechanical force or an electric field of higher voltage.

17.
Adv Mater ; 31(10): e1807751, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30633403

RESUMO

Functional soft materials exhibiting distinct functionalities in response to a specific stimulus are highly desirable towards the fabrication of advanced devices with superior dynamic performances. Herein, two novel light-driven chiral fluorescent molecular switches have been designed and synthesized that are able to exhibit unprecedented reversible Z/E photoisomerization behavior along with tunable fluorescence intensity in both isotropic and anisotropic media. Cholesteric liquid crystals fabricated using these new fluorescent molecular switches as chiral dopants exhibit reversible reflection color tuning spanning the visible and infrared region of the spectrum. Transparent display devices have been fabricated using both low chirality and high chirality cholesteric films that operate either exclusively in fluorescent mode or in both fluorescent and reflection mode, respectively. The dual mode display device employing short pitch cholesteric film is able to function on demand under all ambient light conditions including daylight and darkness with fast response and high resolution. Moreover, the proof-of-concept for a "remote-writing board" using cholesteric films containing one of the light-driven chiral fluorescent molecular switches with ease of fabrication and operation is disclosed herein. Such optically rewritable transparent display devices enabled by light-driven chiral fluorescent molecular switches pave a new way for developing novel display technology under different lighting conditions.

18.
Chemistry ; 25(6): 1369-1378, 2019 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-30076632

RESUMO

Owing to their dynamic attributes, non-covalent supramolecular interactions have enabled a new paradigm in the design and fabrication of multifunctional material systems with programmable properties, performances, and reconfigurable traits. Recently, the "halogen bond" has become an enticing supramolecular synthetic tool that displays a plethora of promising and advantageous characteristics. Consequently, this versatile and dynamic non-covalent interaction has been extensively harnessed in various fields such as crystal engineering, self-assembly, materials science, polymer chemistry, biochemistry, medicinal chemistry and nanotechnology. In recent years, halogen bonding has emerged as a tunable supramolecular synthetic tool in the design of functional liquid-crystalline materials with adjustable phases and properties. In this Concept article, the use of halogen bond in the field of stimuli-responsive smart soft materials, that is, liquid crystals is discussed. The design, synthesis and characterization of molecular and macromolecular liquid crystalline materials are described and the modulation of their properties has been emphasized. The power of halogen bonding in offering a large variety of functional liquid crystalline materials from readily accessible mesomorphic and non-mesomorphic complementary building blocks is highlighted. The article concludes with a perspective on the challenges and opportunities in this emerging endeavor towards the realization of enabling and elegant dynamic functional materials.

19.
Adv Mater ; 31(7): e1806172, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-30570775

RESUMO

The ability to control light direction with tailored precision via facile means is long-desired in science and industry. With the advances in optics, a periodic structure called diffraction grating gains prominence and renders a more flexible control over light propagation when compared to prisms. Today, diffraction gratings are common components in wavelength division multiplexing devices, monochromators, lasers, spectrometers, media storage, beam steering, and many other applications. Next-generation optical devices, however, demand nonmechanical, full and remote control, besides generating higher than 1D diffraction patterns with as few optical elements as possible. Liquid crystals (LCs) are great candidates for light control since they can form various patterns under different stimuli, including periodic structures capable of behaving as diffraction gratings. The characteristics of such gratings depend on several physical properties of the LCs such as film thickness, periodicity, and molecular orientation, all resulting from the internal constraints of the sample, and all of these are easily controllable. In this review, the authors summarize the research and development on stimuli-controllable diffraction gratings and beam steering using LCs as the active optical materials. Dynamic gratings fabricated by applying external field forces or surface treatments and made of chiral and nonchiral LCs with and without polymer networks are described. LC gratings capable of switching under external stimuli such as light, electric and magnetic fields, heat, and chemical composition are discussed. The focus is on the materials, designs, applications, and future prospects of diffraction gratings using LC materials as active layers.

20.
Adv Mater ; 30(25): e1706512, 2018 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-29603448

RESUMO

Supramolecular and macromolecular functional helical superstructures are ubiquitous in nature and display an impressive catalog of intriguing and elegant properties and performances. In materials science, self-organized soft helical superstructures, i.e., cholesteric liquid crystals (CLCs), serve as model systems toward the understanding of morphology- and orientation-dependent properties of supramolecular dynamic helical architectures and their potential for technological applications. Moreover, most of the fascinating device applications of CLCs are primarily determined by different orientations of the helical axis. Here, the control of the helical axis orientation of CLCs and its dynamic switching in two and three dimensions using different external stimuli are summarized. Electric-field-, magnetic-field-, and light-irradiation-driven orientation control and reorientation of the helical axis of CLCs are described and highlighted. Different techniques and strategies developed to achieve a uniform lying helix structure are explored. Helical axis control in recently developed heliconical cholesteric systems is examined. The control of the helical axis orientation in spherical geometries such as microdroplets and microshells fabricated from these enticing photonic fluids is also explored. Future challenges and opportunities in this exciting area involving anisotropic chiral liquids are then discussed.

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