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1.
Adv Mater ; 36(27): e2312382, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38632844

RESUMO

Metal-organic frameworks (MOFs) are promising materials for gas sensing but are often limited to single-use detection. A hybridization strategy is demonstrated synergistically deploying conductive MOFs (cMOFs) and conductive polymers (cPs) as two complementary mixed ionic-electronic conductors in high-performing stand-alone chemiresistors. This work presents significant improvement in i) sensor recovery kinetics, ii) cycling stability, and iii) dynamic range at room temperature. The effect of hybridization across well-studied cMOFs is demonstrated based on 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7,10,11-hexaiminotriphenylene (HITP) ligands with varied metal nodes (Co, Cu, Ni). A comprehensive mechanistic study is conducted to relate energy band alignments at the heterojunctions between the MOFs and the polymer with sensing thermodynamics and binding kinetics. The findings reveal that hole enrichment of the cMOF component upon hybridization leads to selective enhancement in desorption kinetics, enabling significantly improved sensor recovery at room temperature, and thus long-term response retention. This mechanism is further supported by density functional theory calculations on sorbate-analyte interactions. It is also found that alloying cPs and cMOFs enables facile thin film co-processing and device integration, potentially unlocking the use of these hybrid conductors in diverse electronic applications.

2.
Nat Commun ; 15(1): 1215, 2024 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-38331971

RESUMO

Tissue adhesives are promising alternatives to sutures and staples for joining tissues, sealing defects, and immobilizing devices. However, existing adhesives mostly take the forms of glues or hydrogels, which offer limited versatility. We report a direct-ink-write 3D printable tissue adhesive which can be used to fabricate bioadhesive patches and devices with programmable architectures, unlocking new potential for application-specific designs. The adhesive is conformable and stretchable, achieves robust adhesion with wet tissues within seconds, and exhibits favorable biocompatibility. In vivo rat trachea and colon defect models demonstrate the fluid-tight tissue sealing capability of the printed patches, which maintained adhesion over 4 weeks. Moreover, incorporation of a blood-repelling hydrophobic matrix enables the printed patches to seal actively bleeding tissues. Beyond wound closure, the 3D printable adhesive has broad applicability across various tissue-interfacing devices, highlighted through representative proof-of-concept designs. Together, this platform offers a promising strategy toward developing advanced tissue adhesive technologies.


Assuntos
Adesivos Teciduais , Ratos , Animais , Adesivos Teciduais/química , Adesivos , Hidrogéis/química , Tecnologia
3.
ACS Sens ; 8(10): 3687-3692, 2023 10 27.
Artigo em Inglês | MEDLINE | ID: mdl-37721017

RESUMO

We present a thermally stable, mechanically compliant, and sensitive polymer-based NO2 gas sensor design. Interconnected nanoscale morphology driven from spinodal decomposition between conjugated polymers tethered with polar side chains and thermally stable matrix polymers offers judicious design of NO2-sensitive and thermally tolerant thin films. The resulting chemiresitive sensors exhibit stable NO2 sensing even at 170 °C over 6 h. Controlling the density of polar side chains along conjugated polymer backbone enables optimal design for coupling high NO2 sensitivity, selectivity, and thermal stability of polymer sensors. Lastly, thermally stable films are used to implement chemiresistive sensors onto flexible and heat-resistant substrates and demonstrate a reliable gas sensing response even after 500 bending cycles at 170 °C. Such unprecedented sensor performance as well as environmental stability are promising for real-time monitoring of gas emission from vehicles and industrial chemical processes.


Assuntos
Temperatura Alta , Dióxido de Nitrogênio , Polímeros
4.
Nat Mater ; 22(7): 895-902, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37322141

RESUMO

Owing to the unique combination of electrical conductivity and tissue-like mechanical properties, conducting polymer hydrogels have emerged as a promising candidate for bioelectronic interfacing with biological systems. However, despite the recent advances, the development of hydrogels with both excellent electrical and mechanical properties in physiological environments is still challenging. Here we report a bi-continuous conducting polymer hydrogel that simultaneously achieves high electrical conductivity (over 11 S cm-1), stretchability (over 400%) and fracture toughness (over 3,300 J m-2) in physiological environments and is readily applicable to advanced fabrication methods including 3D printing. Enabled by these properties, we further demonstrate multi-material 3D printing of monolithic all-hydrogel bioelectronic interfaces for long-term electrophysiological recording and stimulation of various organs in rat models.


Assuntos
Hidrogéis , Polímeros , Animais , Ratos , Condutividade Elétrica , Impressão Tridimensional
5.
Small ; 19(18): e2207554, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36734196

RESUMO

Iono-electronics, that is, transducing devices able to translate ionic injection into electrical output, continue to demand a variety of mixed ionic-electronic conductors (MIECs). Though polar sidechains are widely used in designing novel polymer MIECs, it remains unclear to chemists how much balance is needed between the two antagonistic modes of transport (ion permeability and electronic charge transport) to yield high-performance materials. Here, the impact of molecularly hybridizing ion permeability and charge mobility in semiconducting polymers on their performance in electrochemical and synaptic transistors is investigated. A series of diketopyrrolopyrrole (DPP)-based copolymers are employed to demonstrate the multifunctionality attained by controlling the density of polar sidechains along the backbone. Notably, efficient electrochemical signal transduction and reliable synaptic plasticity are demonstrated via controlled ion insertion and retention. The newly designed DPP-based copolymers further demonstrate unprecedented thermal tolerance among organic mixed ionic-electronic conductors, a key property in the manufacturing of organic electronics.

6.
Nat Biomed Eng ; 6(10): 1118-1133, 2022 10.
Artigo em Inglês | MEDLINE | ID: mdl-35788686

RESUMO

Diabetic foot ulcers and other chronic wounds with impaired healing can be treated with bioengineered skin or with growth factors. However, most patients do not benefit from these treatments. Here we report the development and preclinical therapeutic performance of a strain-programmed patch that rapidly and robustly adheres to diabetic wounds, and promotes wound closure and re-epithelialization. The patch consists of a dried adhesive layer of crosslinked polymer networks bound to a pre-stretched hydrophilic elastomer backing, and implements a hydration-based shape-memory mechanism to mechanically contract diabetic wounds in a programmable manner on the basis of analytical and finite-element modelling. In mouse and human skin, and in mini-pigs and humanized mice, the patch enhanced the healing of diabetic wounds by promoting faster re-epithelialization and angiogenesis, and the enrichment of fibroblast populations with a pro-regenerative phenotype. Strain-programmed patches might also be effective for the treatment of other forms of acute and chronic wounds.


Assuntos
Diabetes Mellitus , Pé Diabético , Humanos , Animais , Camundongos , Suínos , Porco Miniatura , Cicatrização , Pé Diabético/tratamento farmacológico , Pé Diabético/metabolismo , Elastômeros , Polímeros/uso terapêutico
7.
ACS Appl Mater Interfaces ; 11(29): 26204-26212, 2019 Jul 24.
Artigo em Inglês | MEDLINE | ID: mdl-31259517

RESUMO

Stretchable electrode is an essential part of soft electronic devices. Practical stretchable electrodes must meet the following requirements: metallic conductivity and no resistance change in various situations such as repeated large deformation, toxic environment, and large temperature change. This study suggests a simple electrode design that meets all of these requirements simultaneously. The electrode consists of a liquid metal (LM) mesh pattern that is sandwiched between a thermoplastic block copolymer (BCP) film and a BCP/Ag flake composite film with a microfibril network structure on its surface. The electrode has a high conductivity (1.2 × 104 S/cm) and is stretchable up to 600% uniaxial strain (ε). Its resistance remains unchanged during repeated stretching cycles at ε = 300% (ΔR < 0.04 Ω) as well as under simultaneous situation of large deformation (ε = 400%) and large temperature change (20-70 °C). The electrode is anticorrosive in an acidic solution owing to the hydrophobic BCP layer that protects the LM from being etched. This study shows the connection of two separate electrodes and complete healing of scratched electrodes by finger pressing. In addition, it demonstrates the fabrication of superstretchable electroluminescence display as an example of potential uses of the electrode.

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