3D printable high-performance conducting polymer hydrogel for all-hydrogel bioelectronic interfaces.

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.

Effect of Aggregation Structure on Capacitive Energy Storage in Conducting Polymer Films.

Conducting polymers (CPs), a significant class of electrochemical capacitor electrode materials, exhibit exceptional capacitive energy storage performance in aqueous electrolytes. Current research primarily concentrates on enhancing the electrical conductivity and capacitive performance of CPs via molecular design and structural control. However, the absence of a comprehensive understanding of the impact of molecular chain spatial order on ion/electron transport and capacitive performance impedes the development and optimization of advanced electrode materials. Here, a solvent treatment strategy is employed to modulate the molecular chain spatial order of PEDOT : PSS films. The results of electrochemical performance tests and Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) show that Poly(3,4-ethylenedioxythiophene) : poly(styrenesulfonic acid) (PEDOT : PSS) films with both face-on and edge-on orientations exhibit exceptional electronic conductivity and ion diffusion efficiency, with capacitive performance 1.33 times higher than that of PEDOT : PSS films with only edge-on orientation. Consequently, molecular chain orientations conducive to charge transport not only enhance inter-chain coupling, but also effectively reduce ion transport resistance, enabling efficient capacitive energy storage. This research provides novel insights for the design and development of higher performance CPs-based electrode materials.

Energy-dependent photoion angular distributions in two-body Coulomb explosions of molecules.

We experimentally study two-body Coulomb explosions of CO2, O2, and CH3Cl molecules in intense femtosecond laser pulses. We observe an obvious variation in the ionic angular distribution of the fragments with respect to the kinetic energy releases (KERs). Using a classical model based on ab initio potential energy curves, we find that the dependence of the ionic angular distribution on the KER is relevant to the fact that the accurate potential energy deviates significantly from the value determined by applying the Coulomb interaction approximation at a relatively small internuclear distance of the molecule. We show that the KER-dependent ionic angular distribution provides an effective way to determine the critical internuclear distance at which the Coulomb interaction approximation holds or breaks down without relying on the knowledge of the accurate potential energy curves.

Portable electrochemical sensing platform based on amidated GO-MOF and PEDOT:PSS for high-efficient detection of ponceau 4R.

A promising electrochemical sensing platform for the detection of ponceau 4R in food has been fabricated based on the carboxylated graphene oxide (GO-COOH), metal-organic framework (MOF) UIO-66-NH2, and poly (3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). To this end GO-COOH was covalently coupled with UIO-66-NH2 through amide reaction, endowing the material (GO-CONH-UIO-66) unique hierarchical pores and high chemical stability and as a result improving the conductivity of MOF and the dispersion of GO. After the addition of PEDOT:PSS into GO-CONH-UIO-66, the continuity and conductivity of the composite (PEDOT:PSS/GO-CONH-UIO-66) have been further enhanced, due to the high conductivity, favorable film-forming, and hydrophilic properties of PEDOT:PSS. Systematic electrochemical experiments confirm that the PEDOT:PSS/GO-CONH-UIO-66/GCE shows satisfactory electrochemical sensing properties towards the detection of ponceau 4R, with a wide linear detection range of 0.01-30 µM, a low limit of detection of 3.33 nM, and a high sensitivity of 0.606 µA µM-1 cm-2. The PEDOT:PSS/GO-CONH-UIO-66 sensing platform was successfully used to detect ponceau 4R in beverage, and the detection results were compared with  high-performance liquid chromatography. As a result, the PEDOT:PSS/GO-CONH-UIO-66 composite shows a promising application prospect for rapid detection of ponceau 4R in food and will play significant role in food safety detection and supervision.

Rare Earth Doping Engineering Tailoring Advanced Oxygen-Vacancy Co3 O4 with Tunable Structures for High-Efficiency Energy Storage.

Co3 O4  with high theoretical capacitance is a promising electrode material for high-end energy applications, yet the unexcited bulk electrochemical activity, low conductivity, and poor kinetics of Co3 O4  lead to unsatisfactory charge storage capacity. For boosting its energy storage capability, rare earth (RE)-doped Co3 O4  nanostructures with abundant oxygen vacancies are constructed by simple, economical, and universal chemical precipitation. By changing different types of RE (RE = La, Yb, Y, Ce, Er, Ho, Nd, Eu) as dopants, the RE-doped Co3 O4  nanostructures can be well transformed from large nanosheets to coiled tiny nanosheets and finally to ultrafine nanoparticles, meanwhile, their specific surface area, pore distribution, the ratio of Co2+ /Co3+ , oxygen vacancy content, crystalline phase, microstrain parameter, and the capacitance performance are regularly affected. Notably, Eu-doped Co3 O4  nanoparticles with good cycle stability show a maximum specific capacitance of 1021.3 F g-1 (90.78 mAh g-1 ) at 2 A g-1 , higher than 388 F g-1 (34.49 mAh g-1 ) of pristine Co3 O4  nanosheets. The assembling asymmetric supercapacitor delivers a high energy density of 48.23 Wh kg-1  at high power density of 1.2 kW kg-1 . These findings denote the significance and great potential of RE-doped Co3 O4  in the development of high-efficiency energy storage.

3D Printing of Robust High-Performance Conducting Polymer Hydrogel-Based Electrical Bioadhesive Interface for Soft Bioelectronics.

Electrical bioadhesive interface (EBI), especially conducting polymer hydrogel (CPH)-based EBI, exhibits promising potential applications in various fields, including biomedical devices, neural interfaces, and wearable devices. However, current fabrication techniques of CPH-based EBI mostly focus on conventional methods such as direct casting, injection, and molding, which remains a lingering challenge for further pushing them toward customized practical bioelectronic applications and commercialization. Herein, 3D printable high-performance CPH-based EBI precursor inks are developed through composite engineering of PEDOT:PSS and adhesive ionic macromolecular dopants within tough hydrogel matrices (PVA). Such inks allow the facile fabrication of high-resolution and programmable patterned EBI through 3D printing. Upon successive freeze-thawing, the as-printed PEDOT:PSS-based EBI simultaneously exhibits high conductivity of 1.2 S m-1 , low interfacial impedance of 20 Ω, high stretchability of 349%, superior toughness of 109 kJ m-3 , and satisfactory adhesion to various materials. Enabled by these advantageous properties and excellent printability, the facile and continuous manufacturing of EBI-based skin electrodes is further demonstrated via 3D printing, and the fabricated electrodes display excellent ECG and EMG signal recording capability superior to commercial products. This work may provide a new avenue for rational design and fabrication of next-generation EBI for soft bioelectronics, further advancing seamless human-machine integration.

Recent advances in metal-organic framework (MOF)-based agricultural sensors for metal ions: a review.

Metal ions have great significance for agricultural development, food safety, and human health. In turn, there exists an imperative need for the development of novel, sensitive, and reliable sensing techniques for various metal ions. Agricultural sensors for the diagnosis of both agricultural safety and nutritional health can establish quality and safety traceability systems of both agro-products and food to guarantee human health, even life safety. Metal-organic frameworks (MOFs) are utilized widely for the design of diversified sensors due to their distinctive structural characteristics and extraordinary optical and electrical properties. To serve agricultural sensors better, this review is dedicated to providing a brief overview of the synthesis of MOFs, the modification of MOFs, the fabrication of MOF-based film electrodes, the applications of MOF-based agricultural sensors for metal ions, which are centered on electrochemical sensors and optical sensors, and current challenges of MOF-based agricultural sensors. In addition, this review also provides potential future opportunities for the development and practical application of agricultural sensors.

Electrochemical determination of benomyl using MWCNTs interspersed graphdiyne as enhanced electrocatalyst.

Graphdiyne (GDY) has attracted a lot of interest in electrochemical sensing application with the advantages of a large conjugation system, porous structure, and high structure defects. Herein, to further improve the sensing effect of GDY, conductive MWCNTs were chosen as the signal accelerator. To get a stable composite material, polydopamine (PDA) was employed as connecting bridge between GDY and MWCNTs-NH2, where DA was firstly polymerized onto GDY, followed by covalently linking MWCNTs-NH2 with PDA through Michael-type reaction. The formed GDY@PDA/MWCNTs-NH2 composite was then explored as an electrochemical sensor for benomyl (Ben) determination. GDY assists the adsorption and accumulation of Ben molecules to the sensing surface, while MWCNTs-NH2 can enhance the electrical conductivity and electrocatalytic activity, all of which contributing to the significantly improved performance. The proposed sensor displays an obvious oxidation peak at 0.72 V (vs. Hg|Hg2Cl2) and reveals a wide linear range from 0.007 to 10.0 µM and a low limit of detection (LOD) of 1.8 nM (S/N = 3) toward Ben detection. In addition, the sensor shows high stability, repeatability, reproducibility, and selectivity. The feasibility of this sensor was demonstrated by detecting Ben in apple and cucumber samples with a recovery of 94-106% and relative standard deviations (RSDs) less than 2.3% (n = 5). A sensitive electrochemical sensing platform was reported for benomyl (Ben) determination based on a highly stable GDY@PDA/MWCNTs-NH2 composite.

Isoindigo-Thiophene D-A-D-Type Conjugated Polymers: Electrosynthesis and Electrochromic Performances.

Four novel isoindigo-thiophene D-A-D-type precursors are synthesized by Stille coupling and electrosynthesized to yield corresponding hybrid polymers with favorable electrochemical and electrochromic performances. Intrinsic structure-property relationships of precursors and corresponding polymers, including surface morphology, band gaps, electrochemical properties, and electrochromic behaviors, are systematically investigated. The resultant isoindigo-thiophene D-A-D-type polymer combines the merits of isoindigo and polythiophene, including the excellent stability of isoindigo-based polymers and the extraordinary electrochromic stability of polythiophene. The low onset oxidation potential of precursors ranges from 1.10 to 1.15 V vs. Ag/AgCl, contributing to the electrodeposition of high-quality polymer films. Further kinetic studies illustrate that isoindigo-thiophene D-A-D-type polymers possess favorable electrochromic performances, including high optical contrast (53%, 1000 nm), fast switching time (0.8 s), and high coloration efficiency (124 cm2 C-1). These features of isoindigo-thiophene D-A-D-type conjugated polymers could provide a possibility for rational design and application as electrochromic materials.

TiO2-MXene/PEDOT:PSS Composite as a Novel Electrochemical Sensing Platform for Sensitive Detection of Baicalein.

In this work, TiO2-MXene/poly (3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) composite was utilized as an electrode material for the sensitive electrochemical detection of baicalein. The in-situ growth of TiO2 nanoparticles on the surface of MXene nanosheets can effectively prevent their aggregation, thus presenting a significantly large specific surface area and abundant active sites. However, the partial oxidation of MXene after calcination could reduce its conductivity. To address this issue, herein, PEDOT:PSS films were introduced to disperse the TiO2-MXene materials. The uniform and dense films of PEDOT:PSS not only improved the conductivity and dispersion of TiO2-MXene but also enhanced its stability and electrocatalytic activity. With the advantages of a composite material, TiO2-MXene/PEDOT:PSS as an electrode material demonstrated excellent electrochemical sensing ability for baicalein determination, with a wide linear response ranging from 0.007 to 10.0 µM and a lower limit of detection of 2.33 nM. Furthermore, the prepared sensor displayed good repeatability, reproducibility, stability and selectivity, and presented satisfactory results for the determination of baicalein in human urine sample analysis.

Nonsequential double ionization driven by inhomogeneous laser fields.

With a three-dimensional classical ensemble method, we theoretically investigated the correlated electron dynamics in nonsequential double ionization (NSDI) driven by the spatially inhomogeneous fields. Our results show that NSDI in the spatially inhomogeneous fields is more efficient than that in the spatially homogeneous fields at the low laser intensities, while at the high intensities NSDI is suppressed as compared to the homogeneous fields. More interestingly, our results show that the electron pairs from NSDI exhibit a much stronger angular correlation in the spatially inhomogeneous fields, especially at the higher laser intensities. The correlated electron momentum distribution shows that in the inhomogeneous fields the electron pairs favor to achieve the same final momentum, and the distributions dominantly are clustered in the more compact regions. It is shown that the electron's momentum is focused by the inhomogeneous fields. The underlying dynamics is revealed by back-tracing the classical trajectories.

Amplified electrochemical determination of niclosamide in food based on carbon nanohorn@MWCNT composite.

In this work, carbon nanohorn (CNH)-decorated multi-walled carbon nanotube (MWCNT) (CNH@MWCNT) composite was prepared and used to modify glass carbon electrode (GCE) as sensitive electrochemical sensor for niclosamide (NA) determination. Herein, the decoration of CNHs induces higher dispersibility for MWCNTs, and endows the composite with better conductivity, larger surface area, and higher catalytic activity, which leads to significantly enhanced electrochemical behavior toward NA oxidation. The parameters such as mass ratios of CNHs and MWCHTs, the amount of composite materials, the accumulation time, and the solution pH are systematically optimized. Under optimized conditions, the developed electrochemical sensor exhibits a low detection limit of 2.0 nM with a wide linear range of 7.0 nM-10.0 µM and high anti-interference ability. In addition, the sensor displays good stability, repeatability, and reproducibility. The feasibility of the assay was verified by testing NA in brown rice and rice field water samples.

Fabrication of rGO/MXene-Pd/rGO hierarchical framework as high-performance electrochemical sensing platform for luteolin detection.

A  nanocomposite of rGO/MXene-Pd/rGO with hierarchical structure based on Ti3C2Tx MXene, Pd nanoparticles, and reduced graphene oxide (rGO) was synthesized by a green approach. Ti3C2Tx MXene decorated with Pd nanoparticles (MXene-Pd) was prepared first. Then, graphene oxide (GO), MXene-Pd, and GO were coated on the surface of the glassy carbon electrode (GCE) in sequence. After each coating of the GO layer, the GO nanosheets were reduced to rGO electrochemically. The fabricated rGO/MXene-Pd/rGO hierarchical framework performs a pie structure with MXene-Pd as the stuffing and rGO nanosheets as the crust, which will be beneficial to the enhancement of its electrochemical sensing performance. As compared with other electrodes, the rGO/MXene-Pd/rGO/GCE exhibited higher electrocatalytic activity and better sensing performance for luteolin detection, with a wide linear range of 6.0 × 10-10 to 8 × 10-7 M and 1.0 × 10-6 to 1.0 × 10-5 M (oxidation peak potential Epa = 0.34 V vs. SCE), a low detection limit of 2.0 × 10-10 M, and a high sensitivity of 112.72 µA µM-1 cm-2. Moreover, the fabricated sensor also showed high selectivity, reproducibility, and repeatability toward the detection of luteolin. The real sample analysis for luteolin in honeysuckle was successfully carried out by rGO/MXene-Pd/rGO and verified with high-performance liquid chromatography (HPLC) analysis techniques with acceptable results. All the above tests indicate the promising application prospect of the rGO/MXene-Pd/rGO framework for luteolin detection in honeysuckle and other herbs containing luteolin.

2D Leaf-Like Structured ZIF-L Embedded Electrochemically Reduced Graphene Oxide Composite as an Electrochemical Sensing Platform for Sensitively Detecting Benomyl.

In this work, a two-dimensional leaf-like framework-L embedded electrochemically reduced graphene oxide (ERGO@ZIF-L) was proposed as an outstanding electrode material for the sensitive electrochemical sensing of benomyl (BM). ZIF-L is surrounded by ERGO, which could effectively ensure the stability and dispersion of ZIF-L. With this unique combination, the prepared ERGO@ZIF-L displayed excellent synergistic characteristics with a large surface area, excellent conductivity, plentiful active sites, and high electrocatalytic properties, thus endowing it with high sensitivity for BM determination. The experimental parameters, such as solution pH, material volume, and accumulation time, were optimized. Under optimal conditions, the BM sensor showed a wide linear range (0.009-10.0 µM) and low-limit detection (3.0 nM). Moreover, the sensor displayed excellent stability, repeatability, and reproducibility, and good anti-interference capability. The method was successfully applied to detect BM in real-world samples.

High-Quality Conjugated Polymers Achieving Ultra-Trace Detection of Cr2O72- in Agricultural Products.

In view of that conjugated polymers (CPs) are an attractive option for constructing high-sensitive Cr2O72- sensors but suffer from lacking a general design strategy, we first proposed a rational structure design of CPs to tailor their sensing properties while validating the structure-to-performance correlation. Short side chains decorated with N and O atoms as recognition groups were instructed into fluorene to obtain monomers Fmoc-Ala-OH and Fmoc-Thr-OH. Additionally, their polymers P(Fmoc-Ala-OH) and P(Fmoc-Thr-OH) were obtained through electrochemical polymerization. P(Fmoc-Ala-OH) and P(Fmoc-Thr-OH) with high polymerization degrees have an excellent selectivity towards Cr2O72- in comparison to other cations and anions. Additionally, their limit of detection could achieve 1.98 fM and 3.72 fM, respectively. Especially, they could realize the trace detection of Cr2O72- in agricultural products (red bean, black bean, and millet). All these results indicate that short side chains decorated with N and O atoms functionalizing polyfluorene enables the ultra-trace detection of Cr2O72-. Additionally, the design strategy will spark new ideas for the construction of highly selective and sensitive Cr2O72- sensors.

Ti3C2TxMXene/nitrogen-doped reduced graphene oxide composite: a high-performance electrochemical sensing platform for adrenaline detection.

Herein, Ti3C2TxMXene/N-doped reduced graphene oxide (MXene/N-rGO) composite was employed as the electrocatalyst to construct a new electrochemical sensing platform for the determination of adrenaline (AD). The MXene/N-rGO was synthesized via a facile one-step hydrothermal method, where ethylenediamine acted as a reducing agent and N source. The doped N in rGO served as a bridge between MXene and rGO through tight hydrogen bonds. Scanning electron microscopy showed that large numbers of MXenes with accordion-like morphology were distributed on the surface of the N-rGO. The MXene/N-rGO composite displayed a synergetic catalytic effect for oxidizing AD, originating from the unique catalytic activity of N-rGO and the large surface area and satisfactory conductivity of MXene. These characteristics of composite material led to a remarkable effect on signal amplification for the detection of AD, with a wide linear range from 10.0 nM to 90.0µM and a low detection limit of 3.0 nM based on a signal to noise ratio of 3. Moreover, the MXene/N-rGO electrode displayed good stability, repeatability, and reproducibility. Additionally, the proposed sensor was successfully applied for voltammetric sensing of AD in urine with recoveries from 97.75% to 103.0%.

MXene/carbon nanohorns decorated with conductive molecularly imprinted poly(hydroxymethyl-3,4-ethylenedioxythiophene) for voltammetric detection of adrenaline.

A novel molecularly imprinted sensor was developed for the voltammetric determination of adrenaline (AD). MXene/carbon nanohorn (MXene/CNH) composite with good electric conductivity and enormous accessible active sites was firstly introduced as catalytic substrate. Subsequently, molecularly imprinted polymer (MIP) film was fabricated in mixed solutions containing hydroxymethyl-3,4-ethylenedioxythiophene (functional monomer) and AD (template) through electro-polymerization process. A molecularly imprinted sensor was formed after removing the template. The morphology and elemental composition of the prepared composites were studied by scanning electron microscopy and X-ray photoelectron spectroscopy. Cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical performance of the molecularly imprinted sensors. Under optimized conditions, the designed sensor displays a wide linear range from 1.0 nM to 60.0 µM and a low limit of detection of 0.3 nM. The developed sensor also presents good selectivity, reproducibility and long-term stability, and satisfactory feasibility in practical sample analysis. MXene/carbon nanohorns decorated with conductive molecularly imprinted poly(hydroxymethyl-3,4-ethylenedioxythiophene) was proposed for highly sensitive and selective detection of adrenaline.

Frustrated double ionization of atoms in strong laser fields.

With a three-dimensional classical ensemble method, we theoretically investigated frustrated double ionization (FDI) of atoms with different laser wavelengths. Our results show that FDI can be more efficiently generated with shorter wavelengths and lower laser intensities. With proper laser parameters more FDI events can be generated than normal double ionization events. The physical condition under which FDI events happen is identified and explained. The energy distribution of the FDI products - atomic ions in highly excited states - shows a sensitive wavelength dependency.

Improving power conversion efficiency in luminescent solar concentrators using nanoparticle fluorescence and scattering.

Large-size luminescent solar concentrators (LSCs), which act as a complement to silicon-based photovoltaic (Si-PV) systems, still suffer from low power conversion efficiency (PCE). How to improve the performance of LSCs, especially large ones, is currently a hot research topic. Traditional LSCs have only a single transmission mode of fluorescence from the luminescent materials to the Si-PV, but here we introduce a new idea to improve the absorption of Si-PV by employing dual transmission modes of both fluorescence and scattering light. To prepare LSCs with dual mode transmission, Si-PV systems are coupled around the edges of a light-harvesting slice, which is prepared by ultraviolet light-induced polymerization of methyl methacrylate (MMA) solution containing both luminescent CsPbBr3 and TiO2 nanocrystals (NCs). When the sun light or incident light is coupled into the light-harvesting slice, CsPbBr3 NCs can convert the incident light into fluorescence, and then partly transmit to Si-PV at the edges, where the light is finally converted into electrical energy. Besides the traditional fluorescence transmission mode, the addition of TiO2 brings another transmission mode, namely the scattering of incident light to Si-PV, leading to an increase in PCE. In comparison to that of pure CsPbBr3-based LSCs without the addition of TiO2 (0.97%), the PCE of TiO2-doped LSCs with a large size of 20 cm × 20 cm is improved to 1.82%. The maximal PCE appears for LSCs with a size of 5 cm × 5 cm, reaching 2.62%. The reported method of dual transmission modes is a new alternative way to improve the performance of LSC devices, which does not need to change the optical properties of luminescent materials. Moreover, the production process is simple, low-cost and suitable for preparing large area LSCs, further promoting the application of LSCs.

Highly fluorescent triazolopyridine-thiophene D-A-D oligomers for efficient pH sensing both in solution and in the solid state.

Conjugated fluorophores have been extensively used for fluorescence sensing of various substances in the field of life processes and environmental science, due to their noninvasiveness, sensitivity, simplicity and rapidity. Most existing conjugated fluorophores exhibit excellent light-emitting performance in dilute solutions, but their properties substantially decrease or even completely vanish due to severe aggregation quenching in the solid state. Herein, we synthesize a series of triazolopyridine-thiophene donor-acceptor-donor (D-A-D) type conjugated molecules with high absolute fluorescence quantum yields (ΦF) ranging from 80% to 89% in solution. These molecules also show unusual light-emitting properties in the solid state with ΦF of up to 26%. We find that owing to the protonation-deprotonation process of the pyridine ring, these compounds display obvious changes in both fluorescence wavelength and intensity upon addition of acids, and these changes can be readily recovered by the successive introduction of bases. By harnessing this phenomenon, we further show that these fluorophores can be employed for efficient and reversible fluorescence sensing of hydrogen ions in a broad pH range (0.0-7.0). With the fabrication of pH testing papers and ink-printed complex patterns including butterflies and letters on substrates, we demonstrate the application of such sensors to fluorescence indication or solid state pH detection for real samples such as volatile acidic/basic gas and water-quality analysis.