Regio- and Diastereoselective Hydrophosphination and Hydroamidation of gem-Difluorocyclopropenes.

In this study, concise, efficient, and modular hydrophosphinylation and hydroamidation of gem-difluorocyclopropenes were disclosed in a mild and transition-metal-free pattern. Through this approach, phosphorus, and nitrogen-containing gem-difluorocyclopropanes were produced in moderate to good yields with excellent regio- and diastereoselectivity. Readily available gem-difluorocyclopropenes and nucleophilic reagents, along with inexpensive inorganic bases, were employed. Multiple synthetic applications, including gram-scale and derivatization reactions and modification of bioactive molecules, were subsequently elaborated.

Contact pressure-guided wearable dual-channel bioimpedance device for continuous hemodynamic monitoring.

Wearable devices for continuous monitoring of arterial pulse waves have the potential to improve the diagnosis, prognosis, and management of cardiovascular diseases. These pulse wave signals are often affected by the contact pressure between the wearable device and the skin, limiting the accuracy and reliability of hemodynamic parameter quantification. Here, we report a continuous hemodynamic monitoring device that enables the simultaneous recording of dual-channel bioimpedance and quantification of pulse wave velocity (PWV) used to calculate blood pressure (BP). Our investigations demonstrate the effect of contact pressure on bioimpedance and PWV. The pulsatile bioimpedance magnitude reached its maximum when the contact pressure approximated the mean arterial pressure of the subject. We employed PWV to continuously quantify BP while maintaining comfortable contact pressure for prolonged wear. The mean absolute error and standard deviation of the error compared to the reference value were determined to be 0.1 ± 3.3 mmHg for systolic BP, 1.3 ± 3.7 mmHg for diastolic BP, and -0.4 ± 3.0 mmHg for mean arterial pressure when measurements were conducted in the lying down position. This research demonstrates the potential of wearable dual-bioimpedance sensors with contact pressure guidance for reliable and continuous hemodynamic monitoring.

Bio-Inspired Interlocking Structures for Enhancing Flexible Coatings Adhesion.

The flexible protective coatings and substrates frequently exhibit unstable bonding in industrial applications. For strong interfacial adhesion of heterogeneous materials and long-lasting adhesion of flexible protective coatings even in harsh corrosive environments. Inspired by the interdigitated structures in Phloeodes diabolicus elytra, a straightforward magnetic molding technique is employed to create an interlocking microarray for reinforced heterogeneous assembly. Benefiting from this bio-inspired microarrays, the interlocking polydimethylsiloxane (PDMS) coating recorded a 270% improvement in tensile adhesion and a 520% increase in shear resistance, approaching the tensile limitation of PDMS. The elastic polyurethane-polyamide (PUPI) coating equipped with interlocking structures demonstrated a robust adhesion strength exceeding 10.8 MPa and is nearly unaffected by the corrosion immersion. In sharp contrast, its unmodified counterpart exhibited low initial adhesion and maintain ≈20% of its adhesion strength after 30 d of immersion. PUPI coating integrated with microarrays exhibits superior resistance to corrosion (30 d, |Z|0.01HZ ≈1010  Ω cm2 , Rct ≈108  Ω cm2 ), cavitation and long-term adhesion retention. These interlocking designs can also be adapted to curved surfaces by 3D printing and enhances heterogeneous assembly of non-bonded materials like polyvinylidene fluoride (PTFE) and PDMS. This bio-inspired interlocking structures offers a solution for durably bonding incompatible interfaces across varied engineering applications.

Ultrasensitive, Multiplexed Buoyant Sensor for Monitoring Cytokines in Biofluids.

Multiplexed quantification of low-abundance protein biomarkers in complex biofluids is important for biomedical research and clinical diagnostics. However, in situ sampling without perturbing biological systems remains challenging. In this work, we report a buoyant biosensor that enables in situ monitoring of protein analytes at attomolar concentrations with a 15 min temporal resolution. The buoyant biosensor implemented with fluorescent nanolabels enabled the ultrasensitive and multiplexed detection and quantification of cytokines. Implementing the biosensor in a digital manner (i.e., counting the individual nanolabels) further improves the low detection limit. We demonstrate that the biosensor enables the detection and quantification of the time-varying concentrations of cytokines (e.g., IL-6 and TNF-α) in macrophage culture media without perturbing the live cells. The easy-to-apply biosensor with attomolar sensitivity and multiplexing capability can enable an in situ analysis of protein biomarkers in various biofluids and tissues to aid in understanding biological processes and diagnosing and treating diverse diseases.

Add-on soft electronic interfaces for continuous cuffless blood pressure monitoring.

Continuous monitoring of arterial blood pressure is clinically important for the diagnosis and management of cardiovascular diseases. Soft electronic devices with skin-like properties show promise in a wide range of applications, including the human-machine interface, the Internet of things, and health monitoring. Here, we report the use of add-on soft electronic interfaces to address the connection challenges between soft electrodes and rigid data acquisition circuitry for bioimpedance monitoring of cardiac signals, including heart rate and cuffless blood pressure. Nanocomposite films in add-on electrodes provide robust electrical and mechanical contact with the skin and the rigid circuitry. We demonstrate bioimpedance sensors composed of add-on electrodes for continuous blood pressure monitoring with high accuracy. Specifically, the bioimpedance collected with add-on nanocomposite electrodes shows a signal-to-noise ratio of 37.0 dB, higher than the ratio of 25.9 dB obtained with standard silver/silver chloride (Ag/AgCl gel) electrodes. Although the sample set is low, the continuously measured systolic and diastolic blood pressure offer accuracy of -2.0 ± 6.3 mmHg and -4.3 ± 3.9 mmHg, respectively, confirming the grade A performance based on the IEEE standard. These results show promise in bioimpedance measurements with add-on soft electrodes for cuffless blood pressure monitoring.

Experiment investigation on effects of elastic modulus on cavitation erosion of silicone rubber.

Research into cavitation phenomena in various fields shows that the elastic modulus of a boundary has a potential impact on cavitation erosion. To obtain the direct relationship between the elastic modulus of the boundary and cavitiation erosion, single-layer samples with different chemical composition and moduli, and double-layer samples with different elastic moduli and the same surface layer material, were prepared with silicone rubber. The results of cavitation experiments on single-layer samples, show that the coating chemical composition and mechanical properties together affect the cavitation morphology of the coating, and dominant factors vary with erosion stage. Through the cavitation test of double-layer samples, it was found that there is a positive correlation between the elastic modulus of the coating and the degree of cavitation. This study helps us to understand the relationship between coating elastic modulus and cavitation more directly, and provides theoretical and technical guidance for the application of anti-cavitation for elastic coating in engineering.

Anticorrosion Coating with Heterogeneous Assembly of Nanofillers Modulated by a Magnetic Field.

An anticorrosive coating with randomly distributed passive barriers and regionally enriched active corrosion inhibitors is developed by integrating mica nanosheets (MNSs) and magnetic-responsive core-shell mesoporous nanoparticles with 2-mercaptobenzothiazole (Fe3O4@mSiO2/MBT) under magnetic field incubation. The bottom enriched Fe3O4@mSiO2/MBT rapidly releases the MBT to form a passivation layer on corrosion sites, enhancing the corrosion inhibition efficiency by 30.36% compared with the control (NP0.7EP-R). The impedance modulus |Z|0.01 Hz of the sample (NP0.7/MNS0.5/EP) increases by five orders of magnitude compared with that of its control (NP0.7/MNS0EP) after 30 days of corrosion immersion. NP0.7/MNS0.5/EP exhibited the lowest corrosion rate (3.984 × 10-5 mm/year) as compared to the other samples. Notably, the coating in a fractured state still maintains superior corrosion inhibition even after 40 day salt spray testing. The differentiated distribution of nanofillers was well confirmed by optical microscopy and SEM-EDS, and the synergistic effect of the active/passive integrated anticorrosive coating with merits of both comprehensive protection and fast responsiveness was systematically explored.

Bio-Inspired Self-Adaptive Nanocomposite Array: From Non-antibiotic Antibacterial Actions to Cell Proliferation.

Pathogenic bacterial infection and poor native tissue integration are two major issues encountered by biomaterial implants and devices, which are extremely hard to overcome within a single surface, especially for those without involvement of antibiotics. Herein, a self-adaptive surface that can transform from non-antibiotic antibacterial actions to promotion of cell proliferation is developed by in situ assembly of bacteriostatic 3,3'-diaminodipropylamine (DADP)-doped zeolitic imidazolate framework-8 (ZIF-8) on bio-inspired nanopillars. Initially, the nanocomposite surface shows impressive antibacterial effects, even under severe bacterial infection, due to the combination of mechano-bactericidal activity from a nanopillar structure and bacteriostatic activity contributed by pH-responsive release of DADP. After the complete degradation of the ZIF-8 layer, the refurbished nanopillars not only can still physically rupture bacterial membrane but also facilitate mammalian cell proliferation, due to the obvious difference in cell size. More strikingly, the nanocomposite surface totally avoids the usage of antibiotics, eradicating the potential risk of antimicrobial resistance, and the surface exhibited excellent histocompatibility and lower inflammatory response properties as revealed by in vivo tests. This type of self-adaptive surface may provide a promising alternative for addressing the intractable implant-associated requirements, where antibiotic-free antibacterial activity and native tissue integration are both highly needed.

Moldable and Transferrable Conductive Nanocomposites for Epidermal Electronics.

Skin-inspired soft and stretchable electronic devices based on functional nanomaterials have broad applications such as health monitoring, human-machine interface, and the Internet of things. Solution-processed conductive nanocomposites have shown great promise as a building block of soft and stretchable electronic devices. However, realizing conductive nanocomposites with high conductivity, electromechanical stability, and low modulus over a large area at sub-100 µm resolution remains challenging. Here, we report a moldable, transferrable, high-performance conductive nanocomposite comprised of an interpenetrating network of silver nanowires and poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate). The stacked structure of the nanocomposite synergistically integrates the complementary electrical and mechanical properties of the individual components. We patterned the nanocomposite via a simple, low-cost micromolding process and then transferred the patterned large-area electrodes onto various substrates to realize soft, skin-interfaced electrophysiological sensors. Electrophysiological signals measured using the nanocomposite electrodes exhibit a higher signal-to-noise ratio than standard gel electrodes. The nanocomposite design and fabrication approach presented here can be broadly employed for soft and stretchable electronic devices.

Nanoengineered Ink for Designing 3D Printable Flexible Bioelectronics.

Flexible electronics require elastomeric and conductive biointerfaces with native tissue-like mechanical properties. The conventional approaches to engineer such a biointerface often utilize conductive nanomaterials in combination with polymeric hydrogels that are cross-linked using toxic photoinitiators. Moreover, these systems frequently demonstrate poor biocompatibility and face trade-offs between conductivity and mechanical stiffness under physiological conditions. To address these challenges, we developed a class of shear-thinning hydrogels as biomaterial inks for 3D printing flexible bioelectronics. These hydrogels are engineered through a facile vacancy-driven gelation of MoS2 nanoassemblies with naturally derived polymer-thiolated gelatin. Due to shear-thinning properties, these nanoengineered hydrogels can be printed into complex shapes that can respond to mechanical deformation. The chemically cross-linked nanoengineered hydrogels demonstrate a 20-fold rise in compressive moduli and can withstand up to 80% strain without permanent deformation, meeting human anatomical flexibility. The nanoengineered network exhibits high conductivity, compressive modulus, pseudocapacitance, and biocompatibility. The 3D-printed cross-linked structure demonstrates excellent strain sensitivity and can be used as wearable electronics to detect various motion dynamics. Overall, the results suggest that these nanoengineered hydrogels offer improved mechanical, electronic, and biological characteristics for various emerging biomedical applications including 3D-printed flexible biosensors, actuators, optoelectronics, and therapeutic delivery devices.

Wearable plasmonic paper-based microfluidics for continuous sweat analysis.

Wearable sweat sensors have the potential to provide clinically meaningful information associated with the health and disease states of individuals. Current sensors mainly rely on enzymes and antibodies as biorecognition elements to achieve specific quantification of metabolite and stress biomarkers in sweat. However, enzymes and antibodies are prone to degrade over time, compromising the sensor performance. Here, we introduce a wearable plasmonic paper-based microfluidic system for continuous and simultaneous quantitative analysis of sweat loss, sweat rate, and metabolites in sweat. Plasmonic sensors based on label-free surface-enhanced Raman spectroscopy (SERS) can provide chemical "fingerprint" information for analyte identification. We demonstrate the sensitive detection and quantification of uric acid in sweat at physiological and pathological concentrations. The well-defined flow characteristics of paper microfluidic devices enable accurate quantification of sweat loss and sweat rate. The wearable plasmonic device is soft, flexible, and stretchable, which can robustly interface with the skin without inducing chemical or physical irritation.

Bioinspired nanopillar surface for switchable mechano-bactericidal and releasing actions.

Constructing safe and effective antibacterial surfaces has continuously received great attention, especially in healthcare-related fields. Bioinspired mechano-bactericidal nanostructure surfaces could serve as a promising strategy to reduce surface bacterial contamination while avoiding the development of antibiotic resistance. Although effective, these nanostructure surfaces are prone to be contaminated by the accumulation of dead bacteria, inevitably compromising their long-term antibacterial activity. Herein, a bioinspired nanopillar surface with both mechano-bactericidal and releasing actions is developed, via grafting zwitterionic polymer (poly(sulfobetaine methacrylate) (PSBMA)) on ZnO nanopillars. Under dry conditions, this nanopillar surface displays remarkable mechano-bactericidal activity, because the collapsed zwitterionic polymer layer makes no essential influence on nanopillar structure. Once being incubated with aqueous solution, the surface could readily detach the killed bacteria and debris, owing to the swelling of the zwitterionic layer. Consequentially, the surface antibacterial performances can be rapidly and controllably switched between mechano-bactericidal action and bacteria-releasing activity, guaranteeing a long-lasting antibacterial performance. Notably, these collaborative antibacterial behaviors are solely based on physical actions, avoiding the risk of triggering bacteria resistance. The resultant nanopillar surface also enjoys the advantages of substrate-independency and good biocompatibility, offering potential antibacterial applications for biomedical devices and hospital surfaces.

Spectrally multiplexed assay using gap enhanced nanoparticle for detection of a myocardial infarction biomarker panel.

Multiplexed assays are essential for the detection of biomarker panels. Differentiating signals from different biomarkers in a single test zone makes the detection more efficient. In this paper, a new method is designed for the synthesis of gap-enhanced nanoparticles (GeNPs) using Raman reporter molecules (RRM) and 6-amino-1-hexanethiol (6-AHT) as the spacer. The GeNPs show a nanometer-size gap, generate strong surface-enhanced Raman scattering (SERS) attributed to the gap, and exhibit discriminative spectral peaks. The strong Au-S bonds on both core and shell sides and the covalent bond between RRM and 6-AHT led to a stable structure, which ensured the stable SERS signal generation from the GeNPs. Using the GeNPs, a spectrally multiplexed assay for the detection of a biomarker panel is developed. The biomarker panel is composed of cardiac troponin I (cTnI), copeptin, and heart-type fatty acid-binding protein (h-FABP), which improves myocardial infarction (MI) diagnostic performance. A paper-based platform that is more amenable to point-of-care diagnostic analysis is used. The developed single biomarker assay achieves limits of detection of 0.01 ng mL-1, 0.86 ng mL-1, 0.004 ng mL-1 for cTnI, h-FABP, and copeptin in buffer solutions. The dynamic range of the assay in human serum samples also covers the clinically relevant range of the biomarkers. The cross interference in the multiplexed assay is low. These results show the strong potential of the developed GeNPs in multiplexed detection of biomarkers and the developed simple-to-use multiplexed assay in the diagnosis of MI at the point of care.

Printed Ultrastable Bioplasmonic Microarrays for Point-of-Need Biosensing.

Paper-based point-of-need (PON) biosensors are attractive for various applications, including food safety, agriculture, disease diagnosis, and drug screening, owing to their low cost and ease of use. However, existing paper-based biosensors mainly rely on biolabels, colorimetric reagents, and biorecognition elements and exhibit limited stability under harsh environments. Here, we report a label-free paper-based biosensor composed of bioplasmonic microarrays for sensitive detection and quantification of protein targets in small volumes of biofluids. Bioplasmonic microarrays were printed using an ultrastable bioplasmonic ink, rendering the PON sensors excellent thermal, chemical, and biological stability for their reliable performance in resource-limited settings. We fabricated silicone hydrophobic barriers and bioplasmonic microarrays with direct writing and droplet jetting approaches on a three-dimensional (3D) nanoporous paper. Direct writing hydrophobic barriers can define hydrophilic channels less than 100 µm wide. High-resolution patterning of hydrophilic test domains enables the handling and analysis of small fluid volumes. We show that the plasmonic sensors based on a vertical flow assay provide similar sensitivity and low limit of detection with a 60 µL sample volume compared to those with 500 µL samples based on an immersion approach and can shorten assay time from 90 to 20 min.

Circ_0001206 regulates miR-665/CRKL axis to alleviate hypoxia/reoxygenation-induced cardiomyocyte injury in myocardial infarction.

AIMS: Myocardial infarction (MI) is a type of cardiovascular disease caused by myocardial necrosis. Growing evidences have suggested that circular RNAs (circRNAs) play crucial roles in cardiac hypoxia/reoxygenation (H/R)-induced injury of MI. METHODS AND RESULTS: Hypoxia/reoxygenation model of H9C2 cells was established and circ_0001206 expression was detected via quantitative real-time polymerase chain reaction. Ribonuclease R (RNase R) and Actinomycin D (Act D) assays verified the stability. Cell counting kit-8 (CCK-8), western blot, TUNEL, and flow cytometry assays evaluated cell viability and cell apoptosis. RNA pull-down, RNA binding protein immunoprecipitation (RIP), and luciferase reporter assays explored the mechanisms underlying MI. All experimental data were presented with mean ± standard deviation (SD) and P < 0.05 indicated statistical significance. Circ_0001206 was low-expressed in H9C2 cells under H/R treatment. Circ_0001206 was formed by cyclization of CRK like proto-oncogene, adaptor protein (CRKL). Circ_0001206 overexpression promoted cell viability and inhibited cardiomyocyte apoptosis. It was confirmed that circ_0001206 regulated CRKL expression via acting as a competing endogenous RNA (ceRNA) of microRNA-665 (miR-665). CRKL played a protective role in MI. CONCLUSIONS: Circ_0001206 regulates miR-665/CRKL axis to alleviate H/R-induced cardiomyocyte injury in MI. Our findings suggest that circ_0001206 might be a potential target for MI treatment.

Biocompatible mechano-bactericidal nanopatterned surfaces with salt-responsive bacterial release.

Bio-inspired nanostructures have demonstrated highly efficient mechano-bactericidal performances with no risk of bacterial resistance; however, they are prone to become contaminated with the killed bacterial debris. Herein, a biocompatible mechano-bactericidal nanopatterned surface with salt-responsive bacterial releasing behavior is developed by grafting salt-responsive polyzwitterionic (polyDVBAPS) brushes on a bio-inspired nanopattern surface. Benefiting from the salt-triggered configuration change of the grafted polymer brushes, this dual-functional surface shows high mechano-bactericidal efficiency in water (low ionic strength condition), while the dead bacterial residuals can be easily lifted by the extended polymer chains and removed from the surface in 1 M NaCl solution (high ionic strength conditions). Notably, this functionalized nanopatterned surface shows selective biocidal activity between bacterial cells sand eukaryotic cells. The biocompatibility with red blood cells (RBCs) and mammalian cells was tested in vitro. The histocompatibility and prevention of perioperative contamination activity were verified by in vivo evaluation in a rat subcutaneous implant model. This nanopatterned surface with bacterial killing and releasing activities may open new avenues for designing bio-inspired mechano-bactericidal platforms with long-term efficacy, thus presenting a facile alternative in combating perioperative-related bacterial infection. STATEMENT OF SIGNIFICANCE: Bioinspired nanostructured surfaces with noticeable mechano-bactericidal activity showed great potential in moderating drug-resistance. However, the nanopatterned surfaces are prone to be contaminated by the killed bacterial debris and compromised the bactericidal performance. In this study, we provide a dual-functional antibacterial conception with both mechano-bactericidal and bacterial releasing performances not requiring external chemical bactericidal agents. Additionally, this functionalized antibacterial surface also shows selective biocidal activity between bacteria and eukaryotic cells, and the excellent biocompatibility was tested in vitro and in vivo. The new concept for the functionalized mechano-bactericidal surface here illustrated presents a facile antibiotic-free alternative in combating perioperative related bacterial infection in practical application.

Thermoresponsive Nanostructures: From Mechano-Bactericidal Action to Bacteria Release.

Overuse of antibiotics can increase the risk of notorious antibiotic resistance in bacteria, which has become a growing public health concern worldwide. Featured with the merit of mechanical rupture of bacterial cells, the bioinspired nanopillars are promising alternatives to antibiotics for combating bacterial infections while avoiding antibacterial resistance. However, the resident dead bacterial cells on nanopillars may greatly impair their bactericidal capability and ultimately impede their translational potential toward long-term applications. Here, we show that the functions of bactericidal nanopillars can be significantly broadened by developing a hybrid thermoresponsive polymer@nanopillar-structured surface, which retains all of the attributes of pristine nanopillars and adds one more: releasing dead bacteria. We fabricate this surface through coaxially decorating mechano-bactericidal ZnO nanopillars with thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) brushes. Combining the benefits of ZnO nanopillars and PNIPAAm chains, the antibacterial performances can be controllably regulated between ultrarobust mechano-bactericidal action (∼99%) and remarkable bacteria-releasing efficiency (∼98%). Notably, both the mechanical sterilization against the live bacteria and the controllable release for the pinned dead bacteria solely stem from physical actions, stimulating the exploration of intelligent structure-based bactericidal surfaces with persistent antibacterial properties without the risk of triggering drug resistance.

Nanofiber Composite Coating with Self-Healing and Active Anticorrosive Performances.

Synergetic self-healing anticorrosion behaviors, by forming a self-assembly protective layer and repairing coating passive barrier, exhibit great potential in handling the notorious metal corrosion phenomenon. Herein, we developed a nanofiber-supported anticorrosion coating with synergistic protection effects of both self-healing and active corrosion inhibition, via a facile electrospinning combined coating technique. Polycaprolactone (PCL) nanofiber integrated with 2-mecapobenzothiazole-loaded halloysite nanotubes (HNTs-MBT) is directly deposited on the surface of metal substrate, forming an interconnected fiber network framework. The encapsulated corrosion inhibitor MBT can be released by a pH-triggered manner to realize instant corrosion protections. Additionally, coating defects could be repeatedly repaired by continuous polymer fiber upon heat treatment and the anticorrosion efficiency effectively remained, even after three cycles of damage-healing. Moreover, the repaired coating also exhibited durable anticorrosion performance, mainly attributed to the synergetic effects of both thermal-triggered bulk healing and active corrosion inhibition. This type of dual-functional coating provides efficient anticorrosive performances and may show great promise in long-term corrosion protection.

Antifouling Technology Trends in Marine Environmental Protection.

Marine fouling is a worldwide problem, which is harmful to the global marine ecological environment and economic benefits. The traditional antifouling strategy usually uses toxic antifouling agents, which gradually exposes a serious environmental problem. Therefore, green, long-term, broad-spectrum and eco-friendly antifouling technologies have been the main target of engineers and researchers. In recent years, many eco-friendly antifouling technologies with broad application prospects have been developed based on the low toxicity and non-toxicity antifouling agents and materials. In this review, contemporary eco-friendly antifouling technologies and materials are summarized into bionic antifouling and non-bionic antifouling strategies (2000-2020). Non-bionic antifouling technologies mainly include protein resistant polymers, antifoulant releasing coatings, foul release coatings, conductive antifouling coatings and photodynamic antifouling technology. Bionic antifouling technologies mainly include the simulated shark skin, whale skin, dolphin skin, coral tentacles, lotus leaves and other biology structures. Brief future research directions and challenges are also discussed in the end, and we expect that this review would boost the development of marine antifouling technologies.