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A novel stimuli‐responsive hydrogel system with liposomes serving as both noncovalent crosslinkers and functional small molecules carriers for controlled‐release is developed. Liposomes can crosslink polyacrylamide copolymers functionalized with cholesterol‐modified DNA motifs to yield a DNA hydrogel system, due to the hydrophobic interaction between cholesteryl groups and the lipid bilayer of liposomes. Functional information encoded DNA motifs on the polymer backbones endow the hydrogel with programmable smart responsive properties. In a model system, the hydrogel exhibits stimuli‐responsive gel‐to‐sol transformation triggered by the opening of DNA motifs upon the presence of a restriction endonuclease enzyme, EcoR I, or temperature change, realizing the controlled‐release of liposomes which are highly efficient carriers of active small molecules payloads. Two active molecules, 1,1‐dioctadecyl‐3,3,3,3‐tetramethylindodicarbocyanine perchlorate (DiIC18(5)) and calcein, are chosen as the hydrophobic and hydrophilic model payloads, respectively, to address the feasibility of the releasing strategy. Moreover, the hydrogel exhibits injectable property as well as self‐recovery behaviors.  相似文献   

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随着传统硅基电子器件的发展日趋受限,以原子和分子作为电子元器件的研究受到了越来越多的重视.概述了分子电子器件的概念和基本原理,详细介绍了分子导线、分子二极管、分子开关、分子存储器件和分子场效应晶体管的工作原理及最近的研究进展.具有π-共轭结构的有机分子体系是构造分子导线的理想单元;分子结的电子结构不对称性是分子具有整流特性的根本原因;轮烷和索烃是构造分子开关的理想单元之一;分子场效应晶体管的工作原理是量子隧穿,主要是金属-绝缘体-金属间的隧穿效应.最后阐述了目前分子电子器件研究中存在的主要问题.  相似文献   

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Nano‐objects with chiral properties attract growing interest due to their relevance for a wide variety of technological applications. For example, chiral nano‐objects may be used in characterization platforms that involve chiral molecular recognition of proteins or in the fabrication of nanomechanical devices such as screw‐gears or nanoswimmers. Spatial ordering of emitters of circularly polarized light might greatly benefit from the utilization of chiral shapes. Tools developed in DNA nanotechnology now allow precise tailoring of the chiral properties of molecules and materials at various length scales. Among others, they have already been applied to control the handedness of helical shapes (configurational chirality) or the chiral positioning of different‐sized nanoparticles at the vertices of tetrahedra (compositional chirality). This work covers some of the key advances and recent developments in the field of chiral DNA nanoarchitectures and discusses their future perspectives and potential applications.  相似文献   

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It is still very challenging to obtain colorful and long-afterglow room-temperature phosphorescent (RTP) materials from pure organic polymers. Herein, it is found that chitosan (CS), a natural polymer, not only has its own RTP, but also reacts with different phosphorescent molecules to obtain a multicolor, long-afterglow RTP material. CS can emit RTP with a lifetime of 48 ms. In addition, CS is rich in amino groups, and grafting different phosphorescent molecules onto CS by an amidation reaction can modulate it to emit different colors of phosphorescence and obtain a series of colorful CS derivatives. The obtained polymer films also have ultra-long RTP due to the good film-forming ability. In addition, one of the CS derivatives selected with α-cyclodextrin is used to construct RTP materials with lifetimes of up to seconds. The host–guest interactions are used to suppress nonradiative relaxation and build crystalline domains, thus synergistically enhancing the RTP. Interestingly, the RTP properties of the CS derivative films are extremely sensitive to water and heat stimuli, because water broke the hydrogen bonds between adjacent CS molecules and thus altered the rigid environment in the material. Finally, they can be used as a stimuli-responsive ink and for monitoring environmental humidity.  相似文献   

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The immobilization of fluorescent photoinduced electron transfer (PET) switches/sensors into solid state, which usually cannot maintain their identical properties in solution, has remained a big challenge. Herein, a water‐stable anthracene and maleimide appended zirconium‐based‐metal–organic framework (Zr‐MOF; UiO‐68‐An/Ma) is reported. Unlike the regular intramolecular “fluorophore–spacer–receptor” format, the separated immobilization of fluorescent (anthracene) and acceptor (maleimide) groups into the framework of a multivariate MOF can also favor a pseudo‐intramolecular fluorescent PET process, resulting in UiO‐68‐An/Ma with very weak fluorescence. Interestingly, after Diels–Alder reaction or thiol‐ene reaction of maleimide groups, the pseudo‐intramolecular fluorescent PET process in UiO‐68‐An/Ma fails and the solid‐state fluorescence of the crystals is recovered. In addition, UiO‐68‐An/Ma shows an interesting application as solid‐state fluorescent turn‐on sensor for biothiols, with the naked eye response at a low concentration of 50 µmol L?1 within 5 min. This study represents a general strategy to enable the efficient tuning of fluorescent PET switches/sensors in solid state, and considering the fluorescence of the PET‐based MOFs can be restored after addition of analyte/target species, this research will definitely inspire to construct stimuli‐responsive fluorescent MOFs for interesting applications (e.g., logic gate) in future.  相似文献   

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“Paper” has greatly contributed to the development and spread of civilization. Even in today's “digitalized” world, paper continues to play a key role in socioeconomic growth, as is evidenced by the growth in global paper consumption. Unfortunately, the use of paper has its cost in terms of the exhaustion of world's natural resources. Consequently, new, cost‐effective technologies that preserve natural resources are required for this purpose. Functional materials have revolutionized the way people think about developing new technologies. Especially important in this regard are “smart reactive materials,” which are capable of actively responding to external stimuli such as heat, light, mechanical stress, and specific molecular orientations. Moreover, functionalized chromogenic materials, which undergo reversible color switching upon external stimulation, have attracted great attention in the context of developing rewritable paper. Here, investigations of various materials and systems that are devised for use as rewritable paper are reviewed with the hope that the coverage will stimulate and guide future studies in this area.  相似文献   

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The absence of targeted, single treatment methods produces low therapeutic value for treating cancers. To increase the accumulation of drugs in tumors and improve the treatment effectiveness, near‐infrared 808 nm photothermal responsive dual aptamers‐targeted docetaxel (DTX)‐containing nanoparticles is proposed. In this system, DTX and NH4HCO3 are loaded in thermosensitive liposomes. The surface of liposomes is coated with gold nanoshells and connected with sulfydryl (SH? ) modified AS1411 and S2.2 aptamers. The nanosystem has good biocompatibility and uniform size (diameter about 200 nm). The drug is rapidly released, reaching a maximum amount (84%) at 4 h under 808 nm laser irradiation. The experiments conducted in vitro and in vivo demonstrate the nanosystem can synergistically inhibit tumor growth by combination of chemotherapy, photothermal therapy, and biological therapy. Dual ligand functionalization significantly increases cellular uptake on breast cancer cell line (MCF‐7) cells and achieves ultrasound imaging (USI) at tumor site. The results indicate that this drug delivery system is a promising theranostic agent involving light‐thermal response at tumor sites, dual ligand targeted triplex therapy, and USI.  相似文献   

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Recent experiments have shown that the current–voltage characteristics (I–V) of BPDN‐DT (bipyridyl‐dinitro oligophenylene‐ethynylene dithiol) can be switched in a very controlled manner between “on” and “off” traces by applying a pulse in a bias voltage, Vbias. Here, the polaron formation energies are calculated to check a frequently held belief, namely, that the polaron formation can explain the observed bistability. These results are not consistent with such a mechanism. Instead, a conformational reorientation is proposed. The molecule carries an intrinsic dipole moment, which couples to Vbias. Ramping Vbias exerts a force on the dipole that can reorient (“rotate”) the molecule from the ground state (“off”) into a metastable configuration (“on”) and back. By elaborated electronic structure calculations, a specific path for this rotation is identified through the molecule's conformational phase space. It is shown that this path has sufficiently high barriers to inhibit thermal instability but that the molecule can still be switched in the voltage range of the junction stability. The theoretical I–Vs qualitatively reproduce the key experimental observations. A proposal for the experimental verification of the alternative mechanism of conductance switching is presented.  相似文献   

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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.  相似文献   

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The ability of electronic devices to act as switches makes digital information processing possible. Succeeding graphene, emerging inorganic 2D materials (i2DMs) have been identified as alternative 2D materials to harbor a variety of active molecular components to move the current silicon-based semiconductor technology forward to a post-Moore era focused on molecule-based information processing components. In this regard, i2DMs benefits are not only for their prominent physiochemical properties (e.g., the existence of bandgap), but also for their high surface-to-volume ratio rich in reactive sites. Nonetheless, since this field is still in an early stage, having knowledge of both i) the different strategies for molecularly functionalizing the current library of i2DMs, and ii) the different types of active molecular components is a sine qua non condition for a rational design of stimuli-responsive i2DMs capable of performing logical operations at the molecular level. Consequently, this Review provides a comprehensive tutorial for covalently anchoring ad hoc molecular components—as active units triggered by different external inputs—onto pivotal i2DMs to assess their role in the expanding field of molecule-programmable nanoelectronics for electrically monitoring bistable molecular switches. Limitations, challenges, and future perspectives of this emerging field which crosses materials chemistry with computation are critically discussed.  相似文献   

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A new type of nanoscale bioswitch based on the electrical detection of chemically induced cleavage of chemical bonds, which bind individual nanowires across a pair of electrodes is demonstrated. Carbon nanofibers are manipulated using dielectrophoresis to form single-nanowire bridges across microelectrode junctions, and are anchored through a biomolecular interaction. Once in place, chemically induced cleavage of a recognition site along the bonds linking the nanowire to the electrodes allows the nanowire to be easily removed by a flow of fluid; this removal can be detected in real time via changes in the AC electrical response. This form of sensing is inherently digital in nature as the removal of a single nanowire produces a sudden decrease in the current between electrodes and is essentially a chemoselective fuse. These results suggest that this sensing principle could be a general method for digital chemical and/or biological sensing using individual nanowires.  相似文献   

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The switching behavior of surface-supported molecular units excited by current, light, or mechanical forces is determined by the shape of the adsorption potential. The ability to tailor the energy landscape in which a molecule resides at a surface gives the possibility of imposing a desired response, which is of paramount importance for the realization of molecular electronic units. Here, by means of scanning tunneling microscopy, a triazatruxene (TAT) molecule on Ag(111) is studied, which shows a switching behavior characterized by transitions of the molecule between three states, and which is attributed to three energetically degenerate bonding configurations. Upon tunneling current injection, the system can be excited and continuously driven, showing a switching directionality close to 100%. Two surface enantiomers of TAT show opposite switching directions pointing at the chirality of the energy landscape of the adsorption potential as a key ingredient for directional switching. Further, it is shown that by tuning the tunneling parameters, the symmetry of the adsorption potential can be controllably adjusted, leading to a suppression of the directionality or an inversion of the switching direction. The findings represent a molecule-surface model system exhibiting unprecedented control of the shape of its adsorption potential.  相似文献   

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Developing smart controlled‐release systems for cancer therapy is highly desired in biomedicine. In order to improve therapeutic efficacy and lower undesired side effects, the construction of stimulus‐responsive nanocarriers is a favorable solution. Emerging supramolecular self‐assemblies possessing intrinsic dynamic and adaptive features present promising capabilities for the fabrication of stimulus‐responsive drug‐release systems. Dynamic supramolecular vesicles have attracted considerable attention as therapeutic carriers ascribed to their advantages of high‐cargo‐loading capacity/feasibility, excellent biocompatibility, and facile functionalization. Here, a summary and discussion of recent significant development of vesicles constructed by supramolecular self‐assembly for stimulus‐responsive drug delivery and therapeutics is given. Through presenting some representative studies, strategies regarding the design, synthesis, characterization, and biomedical applications of supramolecular vesicle carriers are highlighted according to various stimulus triggers. The aim is to provide a quick research update in this rapidly developing field.  相似文献   

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