Electrochemical and Electrical Biosensors for Wearable and Implantable Electronics Based on Conducting Polymers and Carbon-Based Materials.

Bioelectronic devices are designed to translate biological information into electrical signals and vice versa, thereby bridging the gap between the living biological world and electronic systems. Among different types of bioelectronics devices, wearable and implantable biosensors are particularly important as they offer access to the physiological and biochemical activities of tissues and organs, which is significant in diagnosing and researching various medical conditions. Organic conducting and semiconducting materials, including conducting polymers (CPs) and graphene and carbon nanotubes (CNTs), are some of the most promising candidates for wearable and implantable biosensors. Their unique electrical, electrochemical, and mechanical properties bring new possibilities to bioelectronics that could not be realized by utilizing metals- or silicon-based analogues. The use of organic- and carbon-based conductors in the development of wearable and implantable biosensors has emerged as a rapidly growing research field, with remarkable progress being made in recent years. The use of such materials addresses the issue of mismatched properties between biological tissues and electronic devices, as well as the improvement in the accuracy and fidelity of the transferred information. In this review, we highlight the most recent advances in this field and provide insights into organic and carbon-based (semi)conducting materials' properties and relate these to their applications in wearable/implantable biosensors. We also provide a perspective on the promising potential and exciting future developments of wearable/implantable biosensors.

Water-Resistance-Based S-Scheme Heterojunction for Deep Mineralization of Toluene.

Deep mineralization of low concentration toluene (C7 H8 ) is one of the most significant but challenging reactions in photocatalysis. It is generally assumed that hydroxyl radicals (⋅OH) as the main reactive species contribute to the enhanced photoactivity, however, it remains ambiguous at this stage. Herein, a S-scheme ZnSn(OH)6 -based heterojunction with AlOOH as water resistant surface layer is in situ designed for tuning the free radical species and achieving deep mineralization of C7 H8 . By employing a combination of in situ DRIFTS and materials characterization techniques, we discover that the dominant intermediates such as benzaldehyde and benzoic acid instead of toxic phenols are formed under the action of holes (h+ ) and superoxide radicals (⋅O2 - ). These dominant intermediates turn out to greatly decrease the ring-opening reaction barrier. This study offers new possibilities for rationally tailoring the active species and thus directionally producing dominant intermediates via designing water resistant surface layer.

Single-Atom Engineering of Covalent Organic Framework for Photocatalytic H2 Production Coupled with Benzylamine Oxidation.

In photocatalysis, reducing the exciton binding energy and boosting the conversion of excitons into free charge carriers are vital to enhance photocatalytic activity. This work presents a facile strategy of engineering Pt single atoms on a 2D hydrazone-based covalent organic framework (TCOF) to promote H2 production coupled with selective oxidation of benzylamine. The optimised TCOF-Pt SA photocatalyst with 3 wt% Pt single atom exhibited superior performance to TCOF and TCOF-supported Pt nanoparticle catalysts. The production rates of H2 and N-benzylidenebenzylamine over TCOF-Pt SA3 are 12.6 and 10.9 times higher than those over TCOF, respectively. Empirical characterisation and theoretical simulation showed that the atomically dispersed Pt is stabilised on the TCOF support through the coordinated N1 -Pt-C2 sites, thereby induing the local polarization and improving the dielectric constant to reach the low exciton binding energy. These phenomena led to the promotion of exciton dissociation into electrons and holes and the acceleration of the separation and transport of photoexcited charge carriers from bulk to the surface. This work provides new insights into the regulation of exciton effect for the design of advanced polymer photocatalysts.

Verifying the Charge-Transfer Mechanism in S-Scheme Heterojunctions Using Femtosecond Transient Absorption Spectroscopy.

The S-scheme heterojunction is flourishing in photocatalysis because it concurrently realizes separated charge carriers and sufficient redox ability. Steady-state charge transfer has been confirmed by other methods. However, an essential part, the transfer dynamics in S-scheme heterojunctions, is still missing. To compensate, a series of cadmium sulfide/pyrene-alt-difluorinated benzothiadiazole heterojunctions were constructed and the photophysical processes were investigated with femtosecond transient absorption spectroscopy. Encouragingly, an interfacial charge-transfer signal was detected in the spectra of the heterojunction, which provides solid evidence for S-scheme charge transfer to complement the results from well-established methods. Furthermore, the lifetime for interfacial charge transfer was calculated to be ca. 78.6 ps. Moreover, the S-scheme heterojunction photocatalysts exhibit higher photocatalytic conversion of 1,2-diols and H2 production rates than bare cadmium sulfide.

Calcination-regulated Microstructures of Donor-Acceptor Polymers towards Enhanced and Stable Photocatalytic H2 O2 Production in Pure Water.

Regulating molecular structure of donor-acceptor (D-A) polymer is a promising strategy to improve photoactivity. Herein, a porous nanorod-like D-A polymer is synthesized via a strategy of supramolecular chemistry combined with subsequent calcination treatment. This polymer consists of benzene rings (D) and triazine (A) that are linked by amido bond (-CONH-). -CONH- further partially cracks into cyano groups (-C≡N) (A) under calcination. The ratio of benzene to triazine could be tuned to adjust the -C≡N content by varying the calcination atmosphere. Such regulation of molecular structure could modulate the band structure of D-A polymer and endow it with unique porous nanorod-like morphology, leading to the achievement of two-electron oxygen reduction and two-electron water oxidation and the improvement of exciton splitting, O2 adsorption and activation. These merits synergistically ensure a highly efficient and stable photocatalytic H2 O2 production in pure water.

A Bifunctional CdS/MoO2 /MoS2 Catalyst Enhances Photocatalytic H2 Evolution and Pyruvic Acid Synthesis.

The best use of photogenerated electrons and holes is crucial to boosting photocatalytic activity. Herein, a bifunctional dual-cocatalyst-modified photocatalyst is constructed based on CdS/MoO2 /MoS2 hollow spheres for hydrogen evolution coupled with selective pyruvic acid (PA) production from lactic acid (LA) oxidation. MoS2 and MoO2 are simultaneously obtained from the conversion of CdMoO4 in one step. In a photocatalytic process, the MoS2 and MoO2 function as the reduction and oxidation centers on which photogenerated electrons and holes accumulate and are used for hydrogen evolution reaction (HER) and PA synthesis, respectively. By monitoring the intermediates, a two-step single-electron route for PA production is proposed, initiated by the cleavage of the α-C(sp3 )-H bond in the LA. The conversion of LA and the selectivity of PA can reach ca. 29 % and 95 % after a five-hour reaction, respectively.

Conspecific odor cues induce different vocal responses in serrate-legged small treefrogs, but only in the absence of acoustic signals.

BACKGROUND: Signal detection is crucial to survival and successful reproduction, and animals often modify behavioral decisions based on information they obtained from the social context. Undeniably, the decision-making in male-male competition and female choice of anurans (frogs and toads) depends heavily on acoustic signals. However, increasing empirical evidence suggests that additional or alternative types of cue (e.g., visual, chemical, and vibratory) can be used to detect, discriminate and locate conspecifics in many anuran species. Nevertheless, few studies have investigated whether conspecific odor cues affect male's calling behavior. In this study, we conducted an experiment to investigate whether and how different chemical cues (male odors, female odors, and stress odors) from conspecifics affect male's calling strategies in serrate-legged small treefrogs (Kurixalus odontotarsus), and whether the combined chemical and acoustic stimuli have additive effects on calling behavior or not. RESULTS: We found that compared with female odors, male K. odontotarsus reduced calling investment in response to male odors or stress odors, in the absence of rival's advertisement calls. When odor stimuli and advertisement calls were presented simultaneously, however, there were no differences in the vocal response of focal males among odor groups. CONCLUSIONS: These results provide evidence that male treefrogs switch calling investment according to different odor cues from conspecifics, and further demonstrate that calling behavior can be affected by chemical cues in anuran species. Our study highlights the potential role of airborne chemical cues in sex identification and contributes to increase our understanding of anuran communication.

Multisensory modalities increase working memory for mating signals in a treefrog.

Animal choruses, such as those found in insects and frogs, are often intermittent. Thus, females sampling males in the chorus might have to remember the location of the potential mates' calls during periods of silence. Although a number of studies have shown that frogs use and prefer multimodal mating signals, usually acoustic plus visual, it is not clear why they do so. Here we tested the hypothesis that preference for multimodal signals over unimodal signals might be due to multimodal signals instantiating longer memories than unimodal signals, particularly during the inter-chorus intervals. We tested this hypothesis in serrate-legged small treefrogs Kurixalus odontotarsus whose males produce advertisement calls accompanied by conspicuous vocal sac inflation. Females were tested with acoustic and acoustic + visual (video of inflating-deflating vocal sac) mating calls. We found that females prefer multimodal calls over unimodal, audio-only calls. Furthermore, multimodal calls are still preferred after a silent period of up to 30 s, a time that spans the average silent period of the chorus. This was not true of unimodal calls. Our results demonstrate that a multimodal signal can engage longer working memory than a unimodal signal, and thus female memory might favour the evolution of multimodal signals in males through sexual selection. Selection might also favour female preference for multimodal signals if longer memory facilitates mate searching and assessment. Our study does not allow us to elucidate the sequence of evolution of this trait and preference.

Enhanced Photocatalytic H2 -Production Activity of CdS Quantum Dots Using Sn2+ as Cocatalyst under Visible Light Irradiation.

Herein, oil-soluble CdS quantum dots (QDs) are first prepared through a solvent-thermal process. Then, oil-soluble CdS QDs are changed into water-soluble QDs via ligand exchange using mercaptopropionic acid as capping agent at pH 13. The photocatalytic performance is investigated under the visible light irradiation using glycerol as sacrificial agent and Sn2+ as cocatalyst. No H2 -production activity is observed for oil-soluble CdS QDs. Water-soluble CdS QDs exhibit significantly enhanced hydrogen evolution rate. When the concentration of cocatalyst Sn2+ increases to 0.2 × 10-3 m, the rate of hydrogen evolution reaches 1.61 mmol g-1 h-1 , which is 24 times higher than that of the pristine water-soluble CdS QDs. The enhanced H2 -production efficiency is attributed to the adsorption of Sn2+ ions on the surface of CdS QDs that are further reduced to Sn atoms by photogenerated electrons. The in situ generated Sn atoms serve as photocatalytic cocatalyst for efficient hydrogen generation.

Male serrate-legged treefrogs adjust competition strategies according to visual or chemical cues from females.

There is increasing evidence that many anurans use multimodal cues to detect, discriminate and/or locate conspecifics and thus modify their behaviors. To date, however, most studies have focused on the roles of multimodal cues in female choice or male-male interactions. In the present study, we conducted an experiment to investigate whether male serrate-legged small treefrogs (Kurixalus odontotarsus) used visual or chemical cues to detect females and thus altered their competition strategies in different calling contexts. Three acoustic stimuli (advertisement calls, aggressive calls and compound calls) were broadcast in a randomized order after a spontaneous period to focal males in one of four treatment groups: combined visual and chemical cues of a female, only chemical cues, only visual cues and a control (with no females). We recorded the vocal responses of the focal males during each 3 min period. Our results demonstrate that males reduce the total number of calls in response to the presence of females, regardless of how they perceived the females. In response to advertisement calls and compound calls, males that perceived females through chemical cues produced relatively fewer advertisement calls but more aggressive calls. In addition, they produced relatively more aggressive calls during the playback of aggressive calls. Taken together, our study suggests that male Kodontotarsus adjust their competition strategies according to the visual or chemical cues of potential mates and highlights the important role of multisensory cues in male frogs' perception of females.

Designing a 0D/2D S-Scheme Heterojunction over Polymeric Carbon Nitride for Visible-Light Photocatalytic Inactivation of Bacteria.

Constructing heterojunctions between two semiconductors with matched band structure is an effective strategy to acquire high-efficiency photocatalysts. The S-scheme heterojunction system has shown great potential in facilitating separation and transfer of photogenerated carriers, as well as acquiring strong photoredox ability. Herein, a 0D/2D S-Scheme heterojunction material involving CeO2 quantum dots and polymeric carbon nitride (CeO2 /PCN) is designed and constructed by in situ wet chemistry with subsequent heat treatment. This S-scheme heterojunction material shows high-efficiency photocatalytic sterilization rate (88.1 %) towards Staphylococcus aureus (S. aureus) under visible-light irradiation (λ≥420 nm), which is 2.7 and 8.2 times that of pure CeO2 (32.2 %) and PCN (10.7 %), respectively. Strong evidence of S-scheme charge transfer path is verified by theoretical calculations, in situ irradiated X-ray photoelectron spectroscopy, and electron paramagnetic resonance.

Nanoconfined Nickel@Carbon Core-Shell Cocatalyst Promoting Highly Efficient Visible-Light Photocatalytic H2 Production.

The realization of large-scale solar hydrogen (H2 ) production relies on the development of high-performance and low-cost photocatalysts driven by sunlight. Recently, cocatalysts have demonstrated immense potential in enhancing the activity and stability of photocatalysts. Hence, the rational design of highly active and inexpensive cocatalysts is of great significance. Here, a facile method is reported to synthesize Ni@C core-shell nanoparticles as a highly active cocatalyst. After merging Ni@C cocatalyst with CdS nanorod (NR), a tremendously enhanced visible-light photocatalytic H2 -production performance of 76.1 mmol g-1 h-1 is achieved, accompanied with an outstanding quantum efficiency of 31.2% at 420 nm. The state-of-art characterizations (e.g., synchrotron-based X-ray absorption near edge structure) and theoretical calculations strongly support the presence of pronounced nanoconfinement effect in Ni@C core-shell nanoparticles, which leads to controlled Ni core size, intimate interfacial contact and rapid charge transfer, optimized electronic structure, and protection against chemical corrosion. Hence, the combination of nanoconfined Ni@C with CdS nanorod leads to significantly improved photocatalytic activity and stability. This work not only for the first time demonstrates the great potential of using highly active and inexpensive Ni@C core-shell structure to replace expensive Pt in photocatalysis but also opens new avenues for synthesizing cocatalyst/photocatalyst hybridized systems with excellent performance by introducing nanoconfinement effect.

PNA versus DNA in electrochemical gene sensing based on conducting polymers: study of charge and surface blocking effects on the sensor signal.

In this communication, we present an in-depth study of DNA/DNA, DNA/PNA and PNA/PNA hybridisation on a conducting polymer-modified electrode, measured by means of electrochemical impedance spectroscopy (EIS). DNA or PNA nucleic base sequence probes (where DNA stands for deoxyribonucleic acid and PNA for peptide nucleic acid) were covalently attached onto the sensor surface. As PNA is a non-charged variant of DNA, we investigate the effects of the surface charge and surface blocking by the surface confined probe/target nucleic bases complexes onto the kinetics of redox reaction of Fe(CN)63-/4- couple occurring at the electrode/solution interface that provides electrochemical readout for hybridisation. A range of hybridisation detection experiments were performed, where the surface charge and surface charge density were varied, through varying the charged nature of the probe and the target (i.e. PNA or DNA) and the density of surface-bound PNA and DNA probes. To further the understanding of these effects on the measured electrochemical signal, kinetic studies of the hybridisation reactions were undertaken, and the equilibrium binding constants and binding rate constants for the hybridisation reactions were obtained. The study provides valuable insights to guide future designs of biosensors.

Hierarchical Porous O-Doped g-C3 N4 with Enhanced Photocatalytic CO2 Reduction Activity.

Artificial photosynthesis of hydrocarbon fuels by utilizing solar energy and CO2 is considered as a potential route for solving ever-increasing energy crisis and greenhouse effect. Herein, hierarchical porous O-doped graphitic carbon nitride (g-C3 N4 ) nanotubes (OCN-Tube) are prepared via successive thermal oxidation exfoliation and curling-condensation of bulk g-C3 N4 . The as-prepared OCN-Tube exhibits hierarchically porous structures, which consist of interconnected multiwalled nanotubes with uniform diameters of 20-30 nm. The hierarchical OCN-Tube shows excellent photocatalytic CO2 reduction performance under visible light, with methanol evolution rate of 0.88 µmol g-1 h-1 , which is five times higher than bulk g-C3 N4 (0.17 µmol g-1 h-1 ). The enhanced photocatalytic activity of OCN-Tube is ascribed to the hierarchical nanotube structure and O-doping effect. The hierarchical nanotube structure endows OCN-Tube with higher specific surface area, greater light utilization efficiency, and improved molecular diffusion kinetics, due to the more exposed active edges and multiple light reflection/scattering channels. The O-doping optimizes the band structure of g-C3 N4 , resulting in narrower bandgap, greater CO2 affinity, and uptake capacity as well as higher separation efficiency of photogenerated charge carriers. This work provides a novel strategy to design hierarchical g-C3 N4 nanostructures, which can be used as promising photocatalyst for solar energy conversion.

Phosphorene Co-catalyst Advancing Highly Efficient Visible-Light Photocatalytic Hydrogen Production.

Transitional metals are widely used as co-catalysts boosting photocatalytic H2 production. However, metal-based co-catalysts suffer from high cost, limited abundance and detrimental environment impact. To date, metal-free co-catalyst is rarely reported. Here we for the first time utilized density functional calculations to guide the application of phosphorene as a high-efficiency metal-free co-catalyst for CdS, Zn0.8 Cd0.2 S or ZnS. Particularly, phosphorene modified CdS shows a high apparent quantum yield of 34.7 % at 420 nm. This outstanding activity arises from the strong electronic coupling between phosphorene and CdS, as well as the favorable band structure, high charge mobility and massive active sites of phosphorene, supported by computations and advanced characterizations, for example, synchrotron-based X-ray absorption near edge spectroscopy. This work brings new opportunities to prepare highly-active, cheap and green photocatalysts.

Hollow Iron-Vanadium Composite Spheres: A Highly Efficient Iron-Based Water Oxidation Electrocatalyst without the Need for Nickel or Cobalt.

Noble-metal-free bimetal-based electrocatalysts have shown high efficiency for water oxidation. Ni and/or Co in these electrocatalysts are essential to provide a conductive, high-surface area and a chemically stable host. However, the necessity of Ni or Co limits the scope of low-cost electrocatalysts. Herein, we report a hierarchical hollow FeV composite, which is Ni- and Co-free and highly efficient for electrocatalytic water oxidation with low overpotential 390 mV (10 mA cm-2 catalytic current density), low Tafel slope of 36.7 mV dec-1 , and a considerable durability. This work provides a novel and efficient catalyst, and greatly expands the scope of low-cost Fe-based electrocatalysts for water splitting without need of Ni or Co.

Shape-dependent photocatalytic hydrogen evolution activity over a Pt nanoparticle coupled g-C3N4 photocatalyst.

Cubic, octahedral and spherical platinum (Pt) nanoparticles (NPs) ex situ supported on a graphitic carbon nitride (g-C3N4) substrate are synthesized using a colloidal adsorption-deposition method for photocatalytic hydrogen evolution reactions. These Pt NPs of different shapes have similar sizes of around 10 nm but have different facets exposed. It is found that the visible-light-driven photocatalytic activities for the Pt/g-C3N4 hybrid photocatalysts follow the order as: cubic Pt/g-C3N4 < octahedral Pt/g-C3N4 < spherical Pt/g-C3N4, revealing the significant cocatalyst shape-sensitive photocatalytic activity in the Pt/g-C3N4 hybrids. This is mainly due to the different surface atomic structures of different exposed facets of Pt NPs, which lead to the disparity of active sites and adsorption energies in photocatalytic reactions.

Ultrasensitive colorimetric detection of 17ß-estradiol: the effect of shortening DNA aptamer sequences.

We report a strategy enabling ultrasensitive colorimetric detection of 17ß-estradiol (E2) in water and urine samples using DNA aptamer-coated gold nanoparticles (AuNPs). Starting from an established sensor format where aggregation is triggered when target-bound aptamers dissociate from AuNP surfaces, we demonstrated that step-change improvements are easily accessible through deletion of excess flanking nucleotides from aptamer sequences. After evaluating the lowest energy two-dimensional configuration of the previously isolated E2 binding 75-mer aptamer (KD ∼25 nM), new 35-mer and 22-mer aptamers were generated with KD's of 14 and 11 nM by simply removing flanking nucleotides on either side of the inner core. The shorter aptamers were found to improve discrimination against other steroidal molecules and to improve colorimetric sensitivity for E2 detection by 25-fold compared with the 75-mer to 200 pM. In comparing the response of all sequences, we find that the excess flanking nucleotides suppress signal transduction by causing target-bound aptamers to remain adhered to AuNPs, which we confirm via surface sensitive electrochemical measurements. However, comparison between the 22-mer and 35-mer systems show that retaining a small number of excess bases is optimal. The performance advances we achieved by specifically considering the signal transduction mechanism ultimately resulted in facile detection of E2 in urine, as well as enabling environmental detection of E2 at levels approaching biological relevance.

Triethanolamine-modified layered double oxide for efficient CO2 capture with low regeneration energy.

Various adsorbents for CO2 capture have been developed to mitigate the greenhouse effect. In this work, a novel CO2 adsorbent was fabricated by depositing triethanolamine (TEOA) onto the surface of nickel-cobalt-aluminum layered double oxide (NiCoAl-LDO) via the impregnation method. The CO2 capacity of the TEOA-LDO composite reached 1.27 mmol/g at 0 °C and 100 kPa, which was twice that of unmodified NiCoAl-LDO. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that the hydroxyl groups (-OH) on the surface of NiCoAl-LDO played a significant role in facilitating CO2 adsorption, similar to CO2 adsorption in the presence of H2O, where CO2 is not converted to carbamates but to bicarbonates through base-catalyzed hydration. This bicarbonate pathway doubles the theoretical amine efficiency, increases the CO2 capacity, and reduces the energy consumption during CO2 desorption. The work provides valuable insights into the development of CO2 adsorbents with high capacity, excellent cycling stability, and low regeneration energy.

Construction of 2D S-Scheme Heterojunction Photocatalyst.

Semiconductor photocatalytic technology holds immense promise for converting sustainable solar energy into chemically storable energy, with significant applications in the realms of energy and the environment. However, the inherent issue of rapid recombination of photogenerated electrons and holes hinders the performance of single photocatalysts. To overcome this challenge, the construction of 2D S-scheme heterojunction photocatalysts emerges as an effective strategy. The deliberate design of dimensionality ensures a substantial interfacial area; while, the S-scheme charge transfer mechanism facilitates efficient charge separation and maximizes redox capabilities. This review commences with a fresh perspective on the charge transfer mechanism in S-scheme heterojunctions, followed by a comprehensive exploration of preparation methods and characterization techniques. Subsequently, the recent advancements in 2D S-scheme heterojunction photocatalysts are summarized. Notably, the mechanism behind activity enhancement is elucidated. Finally, the prospects for the development of 2D S-scheme photocatalysts are presented.