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Protein-based electronic biomaterials represent an attractive alternative to traditional metallic and semiconductor materials due to their environmentally benign production and purification. However, major challenges hindering further development of these materials include (1) limitations associated with processing proteins in organic solvents and (2) difficulties in forming higher-order structures or scaffolds with multilength scale control. This paper addresses both challenges, resulting in the formation of one-dimensional bundles composed of electrically conductive protein nanowires harvested from the microbes Geobacter sulfurreducens and Escherichia coli. Processing these bionanowires from common organic solvents, such as hexane, cyclohexane, and DMF, enabled the production of multilength scale structures composed of distinctly visible pili. Transmission electron microscopy revealed striking images of bundled protein nanowires up to 10 µm in length and with widths ranging from 50-500 nm (representing assembly of tens to hundreds of nanowires). Conductive atomic force microscopy confirmed the presence of an appreciable nanowire conductivity in their bundled state. These results greatly expand the possibilities for fabricating a diverse array of protein nanowire-based electronic device architectures.
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Geobacter , Nanocables , Conductividad Eléctrica , Transporte de Electrón , SolventesRESUMEN
A dry-etching-assisted femtosecond laser lithography technology is proposed to in-site fabricate micro-optical components with an ultra-smooth three-dimensional continuous profile on a non-planar substrate. Owing to the nanometric resolution of femtosecond laser multi-photon polymerization and dry etching, smooth micro-optical components can be realized on hard materials with surface roughness of approximately 1.5 nm. With flexible and arbitrary designability of femtosecond laser lithography, various high-quality micro-optical components are realized on sapphire. These results indicate that dry-etching-assisted femtosecond laser lithography has promising potential for versatile fabrication of arbitrary ultra-smooth micro/nanostructures on hard materials.
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Controllable degradation and excellent biocompatibility during/after a lifetime endow emerging transient electronics with special superiority in implantable biomedical applications. Currently, most of these devices need external power sources, limiting their real-world utilizations. Optimizing existing bioresorbable electronic devices requires natural-material-based construction and, more importantly, diverse or even all-in-one multifunctionalization. Herein, silk-based implantable, biodegradable, and multifunctional systems, self-powered with transient triboelectric nanogenerators (T2 ENGs), for real-time in vivo monitoring and therapeutic treatments of epileptic seizures, are reported. These T2 ENGs are of customizable in vitro/in vivo operating life and biomechanical sensitivity via the adjustments of silk molecular size, surface structuralization, and device configuration. Functions, such as drug delivery and structural-integrity optical readout (parallel to electronic signals), are enabled for localized anti-infection and noninvasive degradation indication, respectively. A proof-of-principle wireless system is built with mobile-device readout and "smart" treatment triggered by specific symptoms (i.e., epilepsy), exhibiting the practical potential of these silk T2 ENGs as self-powered, transient, and multifunctional implantable bioelectronic platforms.
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Suministros de Energía Eléctrica , Electrónica , Animales , Bombyx , Electrónica/instrumentación , Interacciones Hidrofóbicas e Hidrofílicas , Nanopartículas/química , Ratas Sprague-Dawley , Estrés MecánicoRESUMEN
Protein-based electronic materials have numerous potential advantages with respect to sustainability and biocompatibility over electronic materials that are synthesized using harsh chemical processes and/or which contain toxic components. The microorganism Geobacter sulfurreducens synthesizes electrically conductive protein nanowires (e-PNs) with high aspect ratios (3 nm × 10-30 µm) from renewable organic feedstocks. Here, the integration of G. Sulfurreducens e-PNs into poly(vinyl alcohol) (PVA) as a host polymer matrix is described. The resultant e-PN/PVA composites exhibit conductivities comparable to PVA-based composites containing synthetic nanowires. The relationship between e-PN density and conductivity of the resultant composites is consistent with percolation theory. These e-PNs confer conductivity to the composites even under extreme conditions, with the highest conductivities achieved from materials prepared at pH 1.5 and temperatures greater than 100 °C. These results demonstrate that e-PNs represent viable and sustainable nanowire compositions for the fabrication of electrically conductive composite materials.
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Nanocompuestos/química , Nanocables/química , Geobacter/metabolismo , Polímeros/metabolismoRESUMEN
Herein, we report a facile approach for the maskless production of subwavelength-structured antireflective surfaces on sapphire with high and broadband transmittance in the mid-IR: femtosecond laser direct writing assist with wet etching. With this method, inverted pyramid and cone arrays with a pitch of about 2 µm and a total height of near 900 nm on the sapphire were produced. The resulting subwavelength structures greatly suppress specular reflection at normal incidence. The transmission measurements between 3 and 5 µm are in agreement with the simulations performed using VirtualLab, and the transmittance reached a maximum value of 92.5% at 4 µm. The sapphire with subwavelength structures also exhibits angle-independent transmittance characteristics up to a high θ=60°. Therefore, these subwavelength structures on sapphire are of great technological importance in mid-IR optics, especially for the harsh-condition-applicable windows of military mid-IR devices.
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An all-protein single-nanowire optical biosensor is constructed by a facile and general femtosecond laser direct writing approach with nanoscale structural customization. As-formed protein single nanowires show excellent optical properties (fine waveguiding performance and bio-applicable transmission windows), and are utilized as evanescent optical nanobiosensors for label-free biotin detection.
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Técnicas Biosensibles/métodos , Nanocables , Fenómenos Ópticos , Proteínas/química , Animales , Avidina/química , Biotina/química , Bovinos , Rayos Láser , Albúmina Sérica Bovina/química , Factores de TiempoRESUMEN
Small interfering RNA (siRNA) has garnered much attention in recent years as a promising avenue for cancer gene therapy due to its ability to silence disease-related genes. Effective gene silencing is contingent upon the delivery of siRNA into the cytosol of target cells and requires the implementation of delivery systems possessing multiple functionalities to overcome delivery barriers. The present work explores the multifunctional properties and biological activity of a recently developed cationic lipid carrier, (1-aminoethyl)iminobis[N-(oleicylcysteinyl-1-amino-ethyl)propionamide]) (ECO). The physicochemical properties and biological activity of ECO/siRNA nanoparticles were assessed over a range of N/P ratios to optimize the formulation. Potent and sustained luciferase silencing in a U87 glioblastoma cell line was observed, even in the presence of serum proteins. ECO/siRNA nanoparticles exhibited pH-dependent membrane disruption at pH levels corresponding to various stages of the intracellular trafficking pathway. It was found that disulfide linkages created during nanoparticle formation enhanced the protection of siRNA from degradation and facilitated site-specific siRNA release in the cytosol by glutathione-mediated reduction. Confocal microscopy confirmed that ECO/siRNA nanoparticles readily escaped from late endosomes prior to cytosolic release of the siRNA cargo. These results demonstrate that the rationally designed multifunctionality of ECO/siRNA nanoparticles is critical for intracellular siRNA delivery and the continuing development of safe and effective delivery systems.
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Proteínas Sanguíneas/química , Lípidos/química , Nanopartículas/química , Animales , Cationes , Línea Celular Tumoral , Disulfuros/química , Sistemas de Liberación de Medicamentos , Endosomas/metabolismo , Eritrocitos/efectos de los fármacos , Silenciador del Gen , Glutatión/metabolismo , Hemólisis , Humanos , Concentración de Iones de Hidrógeno , Microscopía Confocal , Microscopía Fluorescente , Nanotecnología/métodos , Interferencia de ARN , ARN Interferente Pequeño/metabolismo , RatasRESUMEN
Mechano-sensitive hair-like sensilla (MSHS) have an ingenious and compact three-dimensional structure and have evolved widely in living organisms to perceive multidirectional mechanical signals. Nearly all MSHS are iontronic or electronic, including their biomimetic counterparts. Here, an all-optical mechano-sensor mimicking MSHS is prototyped and integrated based on a thin-walled glass microbubble as a flexible whispering-gallery-mode resonator. The minimalist integrated device has a good directionality of 32.31 dB in the radial plane of the micro-hair and can detect multidirectional displacements and forces as small as 70 nm and 0.9 µN, respectively. The device can also detect displacements and forces in the axial direction of the micro-hair as small as 2.29 nm and 3.65 µN, respectively, and perceive different vibrations. This mechano-sensor works well as a real-time, directional mechano-sensory whisker in a quadruped cat-type robot, showing its potential for innovative mechano-transduction, artificial perception, and robotics applications.
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Robótica , Sensilos , Animales , Cabello , Fenómenos Mecánicos , ElectrónicaRESUMEN
Modification-free biosensing with high specificity and sensitivity is essential for miniaturized, online, integrated, and rapid, or even real-time molecular analyses. However, most optical biosensors are based on surface pre-modification or fluorescent labeling, and have either low sensitivity or low quality factor (Q). To address these difficulties, in this study, an optical sensor prototype was developed with a microbubble optofluidic channel integrated inside a Fabry-Pérot cavity to three-dimensionally tailor the intra-cavity light field via the intra-cavity lensing (microbubble) configuration. A high Q-factor (â¼105), small mode volume, and high light energy density were experimentally achieved with this "stereo-sensor" while maintaining an ultrahigh refractive index (RI) sensitivity (679 nm/RIU) and ultra-small RI resolution (â¼10-7 RIU at 950 nm). Moreover, specific detection of very low concentration of biomolecules (5 fg/mL for human IgG and 0.5 pg/mL for human serum albumin (HSA)) and wide range of protein concentrations (e.g., fg/mL-ng/mL for human IgG and pg/mL-ng/mL for HSA) without probe pre-modification were achieved owing to the RI change specifically associated with the probe-target binding and the corresponding bio-macromolecular conformation change. This modification-free stereosensing scenario is applicable to continuous, real-time, and multiplexed operations, thus showing potential for online, integrated, dynamic, biomolecular analyses in vitro or in vivo, such as the dynamic metabolic analysis of single cells or organoids and point-of-care tests.
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Técnicas Biosensibles , Humanos , Refractometría , Inmunoglobulina GRESUMEN
Herein, tunable protein harmonic diffractive microlenses (PHDMs) have been constructed by femtosecond laser direct writing from bovine serum albumin. With excellent three-dimensional topography, PHDMs show distinct harmonic diffractive features, such as similarly good imaging performance with smaller thickness than refractive lenses and well controlled minus chromatic dispersion compared with simple diffractive lenses (â¼5% focal length shift against â¼21% of the protein Fresnel zone plate with the same radius under light with wavelength 450-659 nm). Owing to the nature of protein molecules as "building blocks," the focal length of the PHDM can be facilely tuned within seconds by changing the pH value (focal length tunability of up to â¼20%).
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Lentes , Microtecnología/instrumentación , Fenómenos Ópticos , Albúmina Sérica Bovina/química , Animales , BovinosRESUMEN
We present novel nanoporous TiO(2)/polyion thin-film-coated long-period fiber grating (LPFG) sensors for the direct measurement of low-molecular-weight chemicals by monitoring the resonance wavelength shift. The hybrid overlay films are prepared by a simple layer-by-layer deposition approach, which is mainly based on the electrostatic interaction of TiO(2) nanoparticles and polyions. By the alternate immersion of LPFG into dispersions of TiO(2) nanoparticles and polyions, respectively, the so-formed TiO(2)/polyion thin film exhibits a unique nanoporous internal structure and has a relative higher refractive index than LPFG cladding. In particular, the porosity of the thin film reduces the diffusion coefficient and enhances the permeability retention of low-molecular-weight analytes within the porous film. The increases in the refractive index of the LPFG overlay results in a distinguished modulation of the resonance wavelength. Therefore, the detection sensitivity of LPFG sensors has been greatly improved, according to theoretical simulation. After the structure of the TiO(2)/polyion thin film was optimized, glucose solutions as an example with a low concentration of 10(-7) M was easily detected and monitored at room temperature.
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Glucosa/análisis , Nanoestructuras/química , Titanio/química , Peso Molecular , Porosidad , Refractometría , Soluciones , Electricidad Estática , Resonancia por Plasmón de Superficie , AguaRESUMEN
With the rapid increase in information density, problems such as signal crosstalk and crossover restrict the further expansion of chip integration levels and packaging density. Based on this, a novel waveguide structure-photonic jumper wire-is proposed here to break through the technical restrictions in waveguide crossing and parallel line wrapping, which hinder the integration of photonic chips. Furthermore, we fabricated the optical overpass to realize a more complex on-chip optical cross-connection. Our method and structure promote a series of practical schemes for improving optical chip integration.
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We have reported first example of 3D hierarchy structure from self-assembly of water-soluble QDs followed by chemical reaction control. After addition of ethylenediaminetetraacetic acid, dipotassium salt dehydrate (EDTA) into L-cysteine-stabilized CdTe QD solution, the color of solution was observed to become lighter and shallower, and finally white precipitates appeared. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results confirm that the morphology transformation from zero dimensional (0D) QDs via two-dimensional (2D) nanoflakes to 3D microflowers occurs among those QD assemblies. Meanwhile, EDX results demonstrate that the as-formed QD-assemblies are not CdTe but CdS. The turnover of chemistry nature from CdTe to CdS after addition of EDTA is mainly due to the oxidation of Te followed by a series of chemical reactions. The photoluminescence (PL) spectroscopy and confocal laser scanning microscopy (CLSM) results reveal that such 3D hierarchy structure of CdS QDs have good optical property.
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Stimulus-responsive optical polymers, especially gels, are enabling new-concept energy-transducing "smart" optics. Full exploitation of their molecule-derived tuning and integration with traditional micro/nano-optics/optoelectronics rely on the implementation of devices by advanced "intelligent" micro/nano-manufacturing technologies, especially photolithographies with wide compatibility. In light of the increasing need for an organic combination of smart optical materials and digital micro/nano-manufacturing, novel "smart" optical micro-switches, namely, stimulus-actuated Mach-Zehnder interferometers as a proof-of-concept demonstration, were prototyped with protein-based hydrogels via aqueous multiphoton femtosecond laser direct writing (FsLDW). Protein-based Mach-Zehnder-interferometric smart optical devices here display a morphological quality sufficient for optical applications (average surface roughness ≤â¼20 nm), nano-precision three-dimensional (3D) geometry of these millimeter-scale devices and purposely structured distribution of photo-crosslinking degree. Moreover, the device configuration was customized with unbalanced branches in which meticulous stimulus-responsive ability can be realized by simply tuning the surrounding chemical stimuli (i.e., Na2SO4 concentration here). The "heterogeneous" configuration with unbalanced branches (i.e., different optical and stimulus-responsive features) exhibits as-designed "smart" switching of propagated near-infrared light (â¼808 nm). These capabilities, along with total biodegradation, indicate the application promise of this gel-based optic construction strategy towards novel "intelligent", bio/eco-friendly, self-tuning or sensing photonic integrated systems like optofluidics.
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Técnicas Biosensibles , Hidrogeles , Interferometría , Rayos Láser , Óptica y FotónicaRESUMEN
Convalescent serum with a high abundance of neutralization IgG is a promising therapeutic agent for rescuing COVID-19 patients in the critical stage. Knowing the concentration of SARS-CoV-2 S1-specific IgG is crucial in selecting appropriate convalescent serum donors. Here, we present a portable microfluidic ELISA technology for rapid (15 min), quantitative, and sensitive detection of anti-SARS-CoV-2 S1 IgG in human serum with only 8 µL sample volume. We first identified a humanized monoclonal IgG that has a high binding affinity and a relatively high specificity towards SARS-CoV-2 S1 protein, which can subsequently serve as the calibration standard of anti-SARS-CoV-2 S1 IgG in serological analyses. We then measured the abundance of anti-SARS-CoV-2 S1 IgG in 16 convalescent COVID-19 patients. Due to the availability of the calibration standard and the large dynamic range of our assay, we were able to identify "qualified donors" for convalescent serum therapy with only one fixed dilution factor (200 ×). Finally, we demonstrated that our technology can sensitively detect SARS-CoV-2 antigens (S1 and N proteins) with pg/mL level sensitivities in 40 min. Overall, our technology can greatly facilitate rapid, sensitive, and quantitative analysis of COVID-19 related markers for therapeutic, diagnostic, epidemiologic, and prognostic purposes.
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Anticuerpos Antivirales/sangre , Betacoronavirus/inmunología , Infecciones por Coronavirus/virología , Ensayo de Inmunoadsorción Enzimática/instrumentación , Inmunoglobulina G/sangre , Técnicas Analíticas Microfluídicas/instrumentación , Neumonía Viral/virología , Adolescente , Adulto , Anticuerpos Antivirales/inmunología , Antígenos Virales/sangre , Antígenos Virales/inmunología , Técnicas Biosensibles/economía , Técnicas Biosensibles/instrumentación , COVID-19 , Infecciones por Coronavirus/terapia , Ensayo de Inmunoadsorción Enzimática/economía , Diseño de Equipo , Humanos , Inmunización Pasiva , Inmunoglobulina G/inmunología , Límite de Detección , Mediciones Luminiscentes/economía , Mediciones Luminiscentes/instrumentación , Técnicas Analíticas Microfluídicas/economía , Persona de Mediana Edad , Pandemias , Neumonía Viral/terapia , SARS-CoV-2 , Factores de Tiempo , Adulto Joven , Sueroterapia para COVID-19RESUMEN
Flexible electronics can serve as powerful tools for biomedical diagnosis and therapies of neurological disorders, particularly for application cases with brain-machine interfaces (BMIs). Existing conformal soft bioelectrodes are applicable for basic electrocorticogram (ECoG) collecting/monitoring. Nevertheless, as an emerging and promising approach, further multidisciplinary efforts are still demanded for in-depth exploitations with these conformal soft electronics toward their practical neurophysiological applications in both scientific research and real-world clinical operation. Here, clinically-friendly silk-supported/delivered soft bioelectronics are developed, and multiple functions and features valuable for customizable intracranial applications (e.g., biocompatible and spontaneously conformal coupling with cortical surface, spatiotemporal ECoG detecting/monitoring, electro-neurophysiological neural stimulating/decoding, controllable loading/delivery of therapeutic molecules, and parallel optical readouts of operating states) are integrated.
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Optofluidics, which integrates microfluidics and micro-optical components, is crucial for optical sensing, fluorescence analysis, and cell detection. However, the realization of an integrated system from optofluidic manipulation and a microfluidic channel is often hampered by the lack of a universal substrate for achieving monolithic integration. In this study, we report on an integrated optofluidic-microfluidic twin channels chip fabricated by one-time exposure photolithography, in which the twin microchannels on both surfaces of the substrate were exactly aligned in the vertical direction. The twin microchannels can be controlled independently, meaning that fluids could flow through both microchannels simultaneously without interfering with each other. As representative examples, a tunable hydrogel microlens was integrated into the optofluidic channel by femtosecond laser direct writing, which responds to the salt solution concentration and could be used to detect the microstructure at different depths. The integration of such optofluidic and microfluidic channels provides an opportunity to apply optofluidic detection practically and may lead to great promise for the integration and miniaturization of Lab-on-a-Chip systems.
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Técnicas Biosensibles/instrumentación , Dispositivos Laboratorio en un Chip , Técnicas Analíticas Microfluídicas/instrumentación , Óptica y Fotónica/instrumentación , Técnicas Biosensibles/métodos , Hidrogeles/química , Rayos Láser , Técnicas Analíticas Microfluídicas/métodos , Óptica y Fotónica/métodosRESUMEN
Silk and silk fibroin, the biomaterial from nature, nowadays are being widely utilized in many cutting-edge micro/nanodevices/systems via advanced micro/nanofabrication techniques. Herein, for the first time to our knowledge, we report aqueous multiphoton lithography of diversiform-regenerated-silk-fibroin-centric inks using noncontact and maskless femtosecond laser direct writing (FsLDW). Initially, silk fibroin was FsLDW-crosslinked into arbitrary two/three-dimensional micro/nanostructures with good elastic properties merely using proper photosensitizers. More interestingly, silk/metal composite micro/nanodevices with multidimension-controllable metal content can be FsLDW-customized through laser-induced simultaneous fibroin oxidation/crosslinking and metal photoreduction using the simplest silk/Ag(+) or silk/[AuCl4](-) aqueous resists. Noticeably, during FsLDW, fibroin functions as biological reductant and matrix, while metal ions act as the oxidant. A FsLDW-fabricated prototyping silk/Ag microelectrode exhibited 10(4)-Ω(-1 ) m(-1)-scale adjustable electric conductivity. This work not only provides a powerful development to silk micro/nanoprocessing techniques but also creates a novel way to fabricate multifunctional metal/biomacromolecule complex micro/nanodevices for applications such as micro/nanoscale mechanical and electrical bioengineering and biosystems.
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Fibroínas/química , Nanoestructuras/química , Animales , Bombyx , Oro/química , Rayos Láser , Plata/química , Espectroscopía Infrarroja por Transformada de FourierRESUMEN
For the first time, proteins, a promising biocompatible and functionality-designable biomacromolecule material, acted as the host material to construct three-dimensional (3D) whispering-gallery-mode (WGM) microlasers by multiphoton femtosecond laser direct writing (FsLDW). Protein/Rhodamine B (RhB) composite biopolymer was used as optical gain medium innovatively. By adopting high-viscosity aqueous protein ink and optimized scanning mode, protein-based WGM microlasers were customized with exquisite true 3D geometry and smooth morphology. Comparable to previously reported artificial polymers, protein-based WGM microlasers here were endowed with valuable performances including steady operation in air and even in aqueous environments, and a higher quality value (Q) of several thousands (without annealing). Due to the "smart" feature of protein hydrogel, lasing spectrum was responsively adjusted by step of ~0.4 nm blueshift per 0.83-mmol/L Na2SO4 concentration change (0 ~ 5-mmol/L in total leading to ~2.59-nm blueshift). Importantly, other performances including Q, FWHM, FSR, peak intensities, exhibited good stability during adjustments. So, these protein-based 3D WGM microlasers might have potential in applications like optical biosensing and tunable "smart" biolasers, useful in novel photonic biosystems and bioengineering.