Biopolymeric photonic structures: design, fabrication, and emerging applications.

Biological photonic structures can precisely control light propagation, scattering, and emission via hierarchical structures and diverse chemistry, enabling biophotonic applications for transparency, camouflaging, protection, mimicking and signaling. Corresponding natural polymers are promising building blocks for constructing synthetic multifunctional photonic structures owing to their renewability, biocompatibility, mechanical robustness, ambient processing conditions, and diverse surface chemistry. In this review, we provide a summary of the light phenomena in biophotonic structures found in nature, the selection of corresponding biopolymers for synthetic photonic structures, the fabrication strategies for flexible photonics, and corresponding emerging photonic-related applications. We introduce various photonic structures, including multi-layered, opal, and chiral structures, as well as photonic networks in contrast to traditionally considered light absorption and structural photonics. Next, we summarize the bottom-up and top-down fabrication approaches and physical properties of organized biopolymers and highlight the advantages of biopolymers as building blocks for realizing unique bioenabled photonic structures. Furthermore, we consider the integration of synthetic optically active nanocomponents into organized hierarchical biopolymer frameworks for added optical functionalities, such as enhanced iridescence and chiral photoluminescence. Finally, we present an outlook on current trends in biophotonic materials design and fabrication, including current issues, critical needs, as well as promising emerging photonic applications.

Simultaneously Regulating the Ion Distribution and Electric Field to Achieve Dendrite-Free Zn Anode.

Rechargeable aqueous Zn-ion batteries are promising candidates for large-scale energy storage systems. However, there are many unresolved problems in commercial Zn foils such as dendrite growth and structural collapse. Herein, Cu mesh modified with CuO nanowires is constructed to simultaneously coordinate the ion distribution and electric field during Zn nucleation and growth. Owing to the improved uniformity of Zn plating and the confined Zn growth in the 3D framework, the prepared Zn anodes can be operated steadily in symmetrical cells for 340 h with a low voltage hysteresis (20 mV). This work can provide a new strategy to design the dendrite-free Zn anodes for practical application.

Interfacial Design of Dendrite-Free Zinc Anodes for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries have rapidly developed recently as promising energy storage devices in large-scale energy storage systems owing to their low cost and high safety. Research on suppressing zinc dendrite growth has meanwhile attracted widespread attention to improve the lifespan and reversibility of batteries. Herein, design methods for dendrite-free zinc anodes and their internal mechanisms are reviewed from the perspective of optimizing the host-zinc interface and the zinc-electrolyte interface. Furthermore, a design strategy is proposed to homogenize zinc deposition by regulating the interfacial electric field and ion distribution during zinc nucleation and growth. This Minireview can offer potential directions for the rational design of dendrite-free zinc anodes employed in aqueous zinc-ion batteries.

Photothermally Active Reduced Graphene Oxide/Bacterial Nanocellulose Composites as Biofouling-Resistant Ultrafiltration Membranes.

Biofouling poses one of the most serious challenges to membrane technologies by severely decreasing water flux and driving up operational costs. Here, we introduce a novel anti-biofouling ultrafiltration membrane based on reduced graphene oxide (RGO) and bacterial nanocellulose (BNC), which incoporates GO flakes into BNC in situ during its growth. In contrast to previously reported GO-based membranes for water treatment, the RGO/BNC membrane exhibited excellent aqueous stability under environmentally relevant pH conditions, vigorous mechanical agitation/sonication, and even high pressure. Importantly, due to its excellent photothermal property, under light illumination, the membrane exhibited effective bactericidal activity, obviating the need for any treatment of the feedwater or external energy. The novel design and in situ incorporation of the membranes developed in this study present a proof-of-concept for realizing new, highly efficient, and environmental-friendly anti-biofouling membranes for water purification.

The Three-Dimensional Dendrite-Free Zinc Anode on a Copper Mesh with a Zinc-Oriented Polyacrylamide Electrolyte Additive.

Rechargeable aqueous zinc-ion batteries have been considered as a promising candidate for next-generation batteries. However, the formation of zinc dendrites are the most severe problems limiting their practical applications. To develop stable zinc metal anodes, a synergistic method is presented that combines the Cu-Zn solid solution interface on a copper mesh skeleton with good zinc affinity and a polyacrylamide electrolyte additive to modify the zinc anode, which can greatly reduce the overpotential of the zinc nucleation and increase the stability of zinc deposition. The as-prepared zinc anodes show a dendrite-free plating/stripping behavior over a wide range of current densities. The symmetric cell using this dendrite-free anode can be cycled for more than 280 h with a very low voltage hysteresis (93.1 mV) at a discharge depth of 80 %. The high capacity retention and low polarization are also realized in Zn/MnO2 full cells.

Environmental Stability of Plasmonic Biosensors Based on Natural versus Artificial Antibody.

Plasmonic biosensors based on the refractive index sensitivity of localized surface plasmon resonance (LSPR) are considered to be highly promising for on-chip and point-of-care biodiagnostics. However, most of the current plasmonic biosensors employ natural antibodies as biorecognition elements, which can easily lose their biorecognition ability upon exposure to environmental stressors (e.g., temperature and humidity). Plasmonic biosensors relying on molecular imprints as recognition elements (artificial antibodies) are hypothesized to be an attractive alternative for applications in resource-limited settings due to their excellent thermal, chemical, and environmental stability. In this work, we provide a comprehensive comparison of the stability of plasmonic biosensors based on natural and artificial antibodies. Although the natural antibody-based plasmonic biosensors exhibit superior sensitivity, their stability (temporal, thermal, and chemical) was found to be vastly inferior to those based on artificial antibodies. Our results convincingly demonstrate that these novel classes of artificial antibody-based plasmonic biosensors are highly attractive for point-of-care and resource-limited conditions where tight control over transport, storage, and handling conditions is not possible.

Plasmonic Biofoam: A Versatile Optically Active Material.

Owing to their ability to confine and manipulate light at the nanoscale, plasmonic nanostructures are highly attractive for a broad range of applications. While tremendous progress has been made in the synthesis of size- and shape-controlled plasmonic nanostructures, their integration with other materials and application in solid-state is primarily through their assembly on rigid two-dimensional (2D) substrates, which limits the plasmonically active space to a few nanometers above the substrate. In this work, we demonstrate a simple method to create plasmonically active three-dimensional biofoams by integrating plasmonic nanostructures with highly porous biomaterial aerogels. We demonstrate that plasmonic biofoam is a versatile optically active platform that can be harnessed for numerous applications including (i) ultrasensitive chemical detection using surface-enhanced Raman scattering; (ii) highly efficient energy harvesting and steam generation through plasmonic photothermal heating; and (iii) optical control of enzymatic activity by triggered release of biomolecules encapsulated within the aerogel. Our results demonstrate that 3D plasmonic biofoam exhibits significantly higher sensing, photothermal, and loading efficiency compared to conventional 2D counterparts. The design principles and processing methodology of plasmonic aerogels demonstrated here can be broadly applied in the fabrication of other functional foams.

Amorphous AlPO4 Layer Coating Vacuum Thermal Reduced SiOx with Fine Silicon Grains to Enhance the Anode Stability.

Micrometer-sized silicon monoxide (SiO) is regarded as a high-capacity anode material with great potential for lithium ion batteries (LIBs). However, the problems of low initial Coulombic efficiency (ICE), poor electrical conductivity, and large volume change of SiO inevitably impede further application. Herein, the vacuum thermal reduced SiOx with amorphous AlPO4 and carbon double-coating layers is used as the ideal anode material in LIBs. The vacuum thermal reduction at low temperature forms fine silicon grains in the internal particles and maintains the external integrity of SiOx particles, contributing to mitigation of the stress intensification and the subsequent design of multifunctional coating. Meanwhile, the innovative introduction of the multifunctional amorphous AlPO4 layer not only improves the ion/electron conduction properties to ensure the fast reversible reaction but also provides a robust protective layer with stable physicochemical characteristics and inhibits the volume expansion effect. The sample of SiOx anode shows an ICE up to 87.6% and a stable cycling of 200 cycles at 1 A g-1 with an initial specific capacity of 1775.8 mAh g-1. In addition, the assembled pouch battery of 1.8 Ah can also ensure a cycling life of over 150 cycles, demonstrating a promising prospect of this optimized micrometer-sized SiOx anode material for industrial applications.

Signal amplification by cyclic extension enables high-sensitivity single-cell mass cytometry.

Mass cytometry uses metal-isotope-tagged antibodies to label targets of interest, which enables simultaneous measurements of ~50 proteins or protein modifications in millions of single cells, but its sensitivity is limited. Here, we present a signal amplification technology, termed Amplification by Cyclic Extension (ACE), implementing thermal-cycling-based DNA in situ concatenation in combination with 3-cyanovinylcarbazole phosphoramidite-based DNA crosslinking to enable signal amplification simultaneously on >30 protein epitopes. We demonstrate the utility of ACE in low-abundance protein quantification with suspension mass cytometry to characterize molecular reprogramming during the epithelial-to-mesenchymal transition as well as the mesenchymal-to-epithelial transition. We show the capability of ACE to quantify the dynamics of signaling network responses in human T lymphocytes. We further present the application of ACE in imaging mass cytometry-based multiparametric tissue imaging to identify tissue compartments and profile spatial aspects related to pathological states in polycystic kidney tissues.

Construction of magnetic covalent organic frameworks functionalized by benzoboroxole for efficient enrichment of glycoproteins in the physiological environment.

To date, the development of highly selective and efficient glycoproteins/peptides enrichment is still a challenge for mass spectrometry-based proteomic analysis. In this work, we reported a novel strategy to prepare a magnetic amide-linked covalent organic framework functionalized by benzoboroxole (denoted as Fe3O4@COF-ABB), which was then used as an adsorbent for the enrichment of glycoproteins. The physical and adsorption properties of Fe3O4@COF-ABB were fully investigated. The Fe3O4@COF-ABB presents a regular core-shell spherical structure, quick magnetic response performance, regular porosity, and multiple binding sites of phenylboronic acid. Taking advantage of these benefits, the synthesized magnetic composites exhibited a superior adsorption capacity (565.8 mg g-1) and high selectivity towards glycoprotein immunoglobulin G (IgG) under physiological state (pH 7.4). Additionally, the adsorbent Fe3O4@COF-ABB could be easily regenerated and reused 5 times with no reduction of enrichment performance. More importantly, the practical applications of Fe3O4@COF-ABB were further demonstrated by the selective adsorption of IgG from human serum. The present work represents a rational design of versatile functionalization of magnetic COFs, which demonstrates an avenue for the selective enrichment and analysis of IgG from real biological sample matrices.

The electrospun polyacrylonitrile/covalent organic framework nanofibers for efficient enrichment of trace sulfonamides residues in food samples.

In this work, the electrospun polyacrylonitrile/covalent organic frameworks Tp-BD nanofibers (PAN/Tp-BD) were synthesized and applied as an adsorbent for thin film microextraction (TFME) of seven sulfonamides in animal derived food samples. The morphology, structure, porosity, and stability of the prepared nanofibers were investigated. The PAN/Tp-BD nanofibers exhibited good chemical stability, high flexibility, porous fibrous structure, and excellent extraction efficiency. Based on the PAN/Tp-BD nanofibers as the adsorbent, a thin film microextraction-high performance liquid chromatography (TFME-HPLC) method for the determination of seven sulfonamides (SAs) in food samples was developed. Under the optimal conditions, the TFME-HPLC exhibited the low limit of detection (0.10-0.18 ng·mL-1), the low limit of quantitation (0.33-0.60 ng·mL-1), the wide linear range (0.5-50 ng·mL-1) with correlation coefficients between 0.994 and 0.998, and good enrichment factors between 39.7 to 170.1 towards 20 ng/mL SAs solution. The relative standard deviation (RSD) was lower than 11% in the interday and intraday analysis. Furthermore, the applicability of PAN/Tp-BD nanofibers was demonstrated for measuring trace SAs residues in the spiked food samples with recoveries ranging from 85.3% to 115.2%. The results demonstrated that the PAN/Tp-BD nanofibers have great potential for the efficient extraction of sulfonamides from complex food samples.

Cobalt-Catalyzed Carbonization Incorporating Disordered Defects in Ordered Graphitic Domains for Fast and Ultrastable Potassium-Ion Battery.

Carbonaceous materials featuring both ordered graphitic structure and disordered defects hold great promise for high-performance K-ion batteries (KIBs) due to the concurrent advantages of high electronic conductivity, fast and reversible K+ intercalation/deintercalation, and abundant active K+ storage sites. However, it has been a lingering problem and remains a big challenge because graphitization and defects are intrinsic trade-off properties of carbonaceous materials. Herein, for the first time, we propose a cobalt-catalyzed carbonization strategy to fabricate porous carbon nanofibers that incorporate disordered defects in graphitic domain layers (PCNFs-DG) for fast and durable K+ storage. The Co catalyst not only ensures the formation of highly graphitized carbon shells around the Co particles but also introduces nanopores and doping defects in the following catalyst removal process. This idea of architecting defected-ordered graphitic carbon engineering guarantees fast reaction kinetics as well as structural stability with negligible interlayer expansion/contraction owing to the uncompromised electronic conductivity, expanded interlayer spacing, and regulated K+ storage mechanism. These appealing features translate to a high reversible capacity of 318.5 mAh g-1 at 100 mA g-1 and ultrahigh stability with almost 100% capacity retention over 2000 cycles in KIBs. This work puts in perspective that defected and ordered carbonaceous materials could be simultaneously achieved, advancing their performance for next-generation energy storage systems.

Plasmonically-enhanced competitive assay for ultrasensitive and multiplexed detection of small molecules.

Novel methods that enable facile, ultrasensitive and multiplexed detection of low molecular weight organic compounds such as metabolites, drugs, additives, and organic pollutants are valuable in biomedical research, clinical diagnosis, food safety and environmental monitoring. Here, we demonstrate a simple, rapid, and ultrasensitive method for detection and quantification of small molecules by implementing a competitive immunoassay with an ultrabright fluorescent nanolabel, plasmonic fluor. Plasmonic-fluor is comprised of a polymer-coated gold nanorod and bovine serum albumin conjugated with molecular fluorophores and biotin. The synthesis steps and fluorescence emission of plasmonic-fluor was characterized by UV-vis spectroscopy, transmission electron microscopy, and fluorescence microscopy. Plasmon-enhanced competitive assay can be completed within 20 min and exhibited more than 30-fold lower limit-of-detection for cortisol compared to conventional competitive ELISA. The plasmon-enhanced competitive immunoassay when implemented as partition-free digital assay enabled further improvement in sensitivity. Further, spatially multiplexed plasmon-enhanced competitive assay enabled the simultaneous detection of two analytes (cortisol and fluorescein). This simple, rapid, and ultrasensitive method can be broadly employed for multiplexed detection of various small molecules in research, in-field and clinical settings.

High-resolution imaging of protein secretion at the single-cell level using plasmon-enhanced FluoroDOT assay.

Secreted proteins mediate essential physiological processes. With conventional assays, it is challenging to map the spatial distribution of proteins secreted by single cells, to study cell-to-cell heterogeneity in secretion, or to detect proteins of low abundance or incipient secretion. Here, we introduce the "FluoroDOT assay," which uses an ultrabright nanoparticle plasmonic-fluor that enables high-resolution imaging of protein secretion. We find that plasmonic-fluors are 16,000-fold brighter, with nearly 30-fold higher signal-to-noise compared with conventional fluorescence labels. We demonstrate high-resolution imaging of different secreted cytokines in the single-plexed and spectrally multiplexed FluoroDOT assay that revealed cellular heterogeneity in secretion of multiple proteins simultaneously. Using diverse biochemical stimuli, including Mycobacterium tuberculosis infection, and a variety of immune cells such as macrophages, dendritic cells (DCs), and DC-T cell co-culture, we demonstrate that the assay is versatile, facile, and widely adaptable for enhancing biological understanding of spatial and temporal dynamics of single-cell secretome.

Plasmonic Fluor-Enhanced Antigen Arrays for High-Throughput, Serological Studies of SARS-CoV-2.

Serological testing for acute infection or prior exposure is critical for patient management and coordination of public health decisions during outbreaks. Current methods have several limitations, including variable performance, relatively low analytical and clinical sensitivity, and poor detection due to antigenic drift. Serological methods for SARS-CoV-2 detection for the ongoing COVID-19 pandemic suffer from several of these limitations and serves as a reminder of the critical need for new technologies. Here, we describe the use of ultrabright fluorescent reagents, Plasmonic Fluors, coupled with antigen arrays that address a subset of these limitations. We demonstrate its application using patient samples in SARS-CoV-2 serological assays. In our multiplexed assay, SARS-CoV-2 antigens were spotted into 48-plex arrays within a single well of a 96-well plate and used to evaluate remnant laboratory samples of SARS-CoV-2 positive patients. Signal-readout was performed with Auragent Bioscience's Empower microplate reader, and microarray analysis software. Sample volumes of 1 µL were used. High sensitivity of the Plasmonic Fluors combined with the array format enabled us to profile patient serological response to eight distinct SARS-CoV-2 antigens and evaluate responses to IgG, IgM, and IgA. Sensitivities for SARS-CoV-2 antigens during the symptomatic state ranged between 72.5 and 95.0%, specificity between 62.5 and 100%, and the resulting area under the curve values between 0.76 and 0.97. Together, these results highlight the increased sensitivity for low sample volumes and multiplex capability. These characteristics make Plasmonic Fluor-enhanced antigen arrays an attractive technology for serological studies for the COVID-19 pandemic and beyond.

Plasmonically Enhanced CRISPR/Cas13a-Based Bioassay for Amplification-Free Detection of Cancer-Associated RNA.

Novel methods that enable sensitive, accurate and rapid detection of RNA would not only benefit fundamental biological studies but also serve as diagnostic tools for various pathological conditions, including bacterial and viral infections and cancer. Although highly sensitive, existing methods for RNA detection involve long turn-around time and extensive capital equipment. Here, an ultrasensitive and amplification-free RNA quantification method is demonstrated by integrating CRISPR-Cas13a system with an ultrabright fluorescent nanolabel, plasmonic fluor. This plasmonically enhanced CRISPR-powered assay exhibits nearly 1000-fold lower limit-of-detection compared to conventional assay relying on enzymatic reporters. Using a xenograft tumor mouse model, it is demonstrated that this novel bioassay can be used for ultrasensitive and quantitative monitoring of cancer biomarker (lncRNA H19). The novel biodetection approach described here provides a rapid, ultrasensitive, and amplification-free strategy that can be broadly employed for detection of various RNA biomarkers, even in resource-limited settings.

Gold Nanorod Size-Dependent Fluorescence Enhancement for Ultrasensitive Fluoroimmunoassays.

Plasmon-enhanced fluorescence (PEF) is a simple and highly effective approach for improving the signal-to-noise ratio and sensitivity of various fluorescence-based bioanalytical techniques. Here, we show that the fluorescence enhancement efficacy of gold nanorods (AuNRs), which are widely employed for PEF, is highly dependent on their absolute dimensions (i.e., length and diameter). Notably, an increase in the dimensions (length × diameter) of the AuNRs from 46 × 14 to 120 × 38 nm2 while holding the aspect ratio constant leads to nearly 300% improvement in fluorescence enhancement efficiency. Further increase in the AuNR size leads to a decrease of the fluorescence enhancement efficiency. Through finite-difference time-domain (FDTD) simulation, we reveal that the size-dependent fluorescence enhancement efficiency of AuNR stems from the size-dependent electromagnetic field around the plasmonic nanostructures. AuNRs with optimal dimensions resulted in a nearly 120-fold enhancement in the ensemble fluorescence emission from molecular fluorophores bound to the surface. These plasmonic nanostructures with optimal dimensions also resulted in a nearly 30-fold improvement in the limit of detection of human interleukin-6 (IL-6) compared to AuNRs with smaller size, which are routinely employed in PEF.

Microneedle patch for the ultrasensitive quantification of protein biomarkers in interstitial fluid.

The detection and quantification of protein biomarkers in interstitial fluid is hampered by challenges in its sampling and analysis. Here we report the use of a microneedle patch for fast in vivo sampling and on-needle quantification of target protein biomarkers in interstitial fluid. We used plasmonic fluor-an ultrabright fluorescent label-to improve the limit of detection of various interstitial fluid protein biomarkers by nearly 800-fold compared with conventional fluorophores, and a magnetic backing layer to implement conventional immunoassay procedures on the patch and thus improve measurement consistency. We used the microneedle patch in mice for minimally invasive evaluation of the efficiency of a cocaine vaccine, for longitudinal monitoring of the levels of inflammatory biomarkers, and for efficient sampling of the calvarial periosteum-a challenging site for biomarker detection-and the quantification of its levels of the matricellular protein periostin, which cannot be accurately inferred from blood or other systemic biofluids. Microneedle patches for the minimally invasive collection and analysis of biomarkers in interstitial fluid might facilitate point-of-care diagnostics and longitudinal monitoring.

A functionalized magnetic covalent organic framework for sensitive determination of trace neonicotinoid residues in vegetable samples.

A functionalized magnetic covalent organic framework containing the nitro groups (Fe3O4@COF-(NO2)2) with core-shell structure was synthesized for magnetic solid phase extraction (MSPE) of six neonicotinoid insecticides residue in vegetable samples. The structure of Fe3O4@COF-(NO2)2 was investigated by various characterization techniques. The Fe3O4@COF-(NO2)2 exhibits the excellent thermal and chemical stability, high surface area (254.72 m2 g-1), total pore volume (0.19 cm3 g-1), high magnetic responsivity (27.7 emu g-1), which can be used as an ideal adsorbent for rapid isolation and enrichment of target analytes. A sensitive method was developed by using Fe3O4@COF-(NO2)2-based MSPE coupled with HPLC with UV detection. It offered good linearity within the range of 0.1-30 ng mL-1, low limits of detection (S/N = 3) of 0.02-0.05 ng mL-1. Furthermore, high enrichment factors of 170-250 for six neonicotinoid insecticides were obtained. The applicability of Fe3O4@COF-(NO2)2 is demonstrated for measuring trace neonicotinoid residues in vegetable samples with satisfactory recoveries, which ranged from 77.5 to 110.2%. The results indicated that the Fe3O4@COF-(NO2)2 microspheres offer great potential for efficient extraction of neonicotinoid insecticides from complex samples.

Refreshable Nanobiosensor Based on Organosilica Encapsulation of Biorecognition Elements.

Implantable and wearable biosensors that enable monitoring of biophysical and biochemical parameters over long durations are highly attractive for early and presymptomatic diagnosis of pathological conditions and timely clinical intervention. Poor stability of antibodies used as biorecognition elements and the lack of effective methods to refresh the biosensors upon demand without severely compromising the functionality of the biosensor remain significant challenges in realizing protein biosensors for long-term monitoring. Here, we introduce a novel method involving organosilica encapsulation of antibodies for preserving their biorecognition capability under harsh conditions, typically encountered during the sensor refreshing process, and elevated temperature. Specifically, a simple aqueous rinsing step using sodium dodecyl sulfate (SDS) solution refreshes the biosensor by dissociating the antibody-antigen interactions. Encapsulation of the antibodies with an organosilica layer is shown to preserve the biorecognition capability of otherwise unstable antibodies during the SDS treatment, thus ultimately facilitating the refreshability of the biosensor over multiple cycles. Harnessing this method, we demonstrate the refreshability of plasmonic biosensors for anti-IgG (model bioanalyte) and neutrophil gelatinase-associated lipocalin (NGAL) (a biomarker for acute and chronic kidney injury). The novel encapsulation approach demonstrated can be easily extended to other transduction platforms to realize refreshable biosensors for monitoring of protein biomarkers over long durations.