Ingenious fluorescent probes for biogenic amine and their applications in bioimaging and food spoilage detection.

Food safety issues have received much attention. Biogenic amines are considered important markers of food spoilage. Accurate detection of biogenic amines is important for food quality monitoring. Herein, we developed two coumarin-difluoroboron ß-diketonate hybrid probes, 1 and 2, for detection of amines. Both probes possess large conjugated structures and donor-acceptor-donor configuration, exhibiting solvatochromic effects due to intramolecular charge transfer mechanism. Upon reaction with amines, the boron atom in difluoroboron unit can interact with lone pair electrons of nitrogen atom, thus resulting in significant changes in absorption and fluorescence properties. These probes were successfully utilized to image amine in live cells and liver tissues. Moreover, by photographing probe-loaded food extract supernatant, we establish the relationship between color parameters and food storage time, which can easily indicate food spoilage process. This work and its findings hold promise for providing potential strategies for real-time and convenient detection of food freshness.

Enhanced Electrochemical CO2 Reduction to Formate over Phosphate-Modified In: Water Activation and Active Site Tuning.

Electrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P-O)δ- modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P-O)δ- has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P-O)δ- modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P-O)δ- modified oxide-derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm-2 and a cathodic potential of -1.2 V vs. RHE in an alkaline electrolyte.

Pysanky to Microfluidics: An Innovative Wax-Based Approach to Low Cost, Rapid Prototyping of Microfluidic Devices.

A wax-based contact printing method to create microfluidic devices is demonstrated. This printing technology demonstrates a new pathway to rapid, cost-effective device prototyping, eliminating the use of expensive micromachining equipment and chemicals. Derived from the traditional Ukrainian Easter egg painting technique called "pysanky" a series of microfluidic devices were created. Pysanky is the use of a heated wax stylus, known as a "kistka", to create micro-sized, intricate designs on the surface of an egg. The proposed technique involves the modification of an x-y-z actuation translation system with a wax extruder tip in junction with Polydimethysiloxane (PDMS) device fabrication techniques. Initial system optimization was performed considering design parameters such as extruder tip size, contact angle, write speed, substrate temperature, and wax temperature. Channels created ranged from 160 to 900 µm wide and 10 to 150 µm high based upon system operating parameters set by the user. To prove the capabilities of this technology, a series of microfluidic mixers were created via the wax technique as well as through traditional photolithography: a spiral mixer, a rainbow mixer, and a linear serial dilutor. A thermo-fluidic computational fluid dynamic (CFD) model was generated as a means of enabling rational tuning, critical to the optimization of systems in both normal and extreme conditions. A comparison between the computational and experimental models yielded a wax height of 57.98 µm and 57.30 µm, respectively, and cross-sectional areas of 11,568 µm2 and 12,951 µm2, respectively, resulting in an error of 1.18% between the heights and 10.76% between the cross-sectional areas. The device's performance was then compared using both qualitative and quantitative measures, considering factors such as device performance, channel uniformity, repeatability, and resolution.

Plasmonic silver and gold nanoparticles: shape- and structure-modulated plasmonic functionality for point-of-caring sensing, bio-imaging and medical therapy.

Silver and gold nanoparticles have found extensive biomedical applications due to their strong localized surface plasmon resonance (LSPR) and intriguing plasmonic properties. This review article focuses on the correlation among particle geometry, plasmon properties and biomedical applications. It discusses how particle shape and size are tailored via controllable synthetic approaches, and how plasmonic properties are tuned by particle shape and size, which are embodied by nanospheres, nanorods, nanocubes, nanocages, nanostars and core-shell composites. This article summarizes the design strategies for the use of silver and gold nanoparticles in plasmon-enhanced fluorescence, surface-enhanced Raman scattering (SERS), electroluminescence, and photoelectrochemistry. It especially discusses how to use plasmonic nanoparticles to construct optical probes including colorimetric, SERS and plasmonic fluorescence probes (labels/reporters). It also demonstrates the employment of Ag and Au nanoparticles in polymer- and paper-based microfluidic devices for point-of-care testing (POCT). In addition, this article highlights how to utilize plasmonic nanoparticles for in vitro and in vivo bio-imaging based on SERS, fluorescence, photoacoustic and dark-field models. Finally, this article shows perspectives in plasmon-enhanced photothermal and photodynamic therapy.

Machine Learning Paves the Way for High Entropy Compounds Exploration: Challenges, Progress, and Outlook.

Machine learning (ML) has emerged as a powerful tool in the research field of high entropy compounds (HECs), which have gained worldwide attention due to their vast compositional space and abundant regulatability. However, the complex structure space of HEC poses challenges to traditional experimental and computational approaches, necessitating the adoption of machine learning. Microscopically, machine learning can model the Hamiltonian of the HEC system, enabling atomic-level property investigations, while macroscopically, it can analyze macroscopic material characteristics such as hardness, melting point, and ductility. Various machine learning algorithms, both traditional methods and deep neural networks, can be employed in HEC research. Comprehensive and accurate data collection, feature engineering, and model training and selection through cross-validation are crucial for establishing excellent ML models. ML also holds promise in analyzing phase structures and stability, constructing potentials in simulations, and facilitating the design of functional materials. Although some domains, such as magnetic and device materials, still require further exploration, machine learning's potential in HEC research is substantial. Consequently, machine learning has become an indispensable tool in understanding and exploiting the capabilities of HEC, serving as the foundation for the new paradigm of Artificial-intelligence-assisted material exploration.

A nanoscale inorganic coating strategy for stabilizing hydrogel neural probes in vivo.

Hydrogels with adaptable optical and mechanical characteristics show considerable promise for light delivery in vivo with neuroengineering applications. However, the unlinked amorphous polymer chains within hydrogels can cause volumetric swelling after water absorption under physiological conditions over time. Chemically cross-linked poly(vinyl alcohol) (PVA) hydrogels showcase fatigue-resistant attributes and promising biocompatibility for the manufacture of soft neural probes. However, possible swelling of the PVA hydrogel matrix could impact the structural stability of hydrogel-based bioelectronics and their long-term in vivo functionality. In this study, we utilized an atomic layer deposition (ALD) technique to generate an inorganic, silicon dioxide (SiO2) coating layer on chemically cross-linked PVA hydrogel fibers. To evaluate the stability of SiO2-coated PVA hydrogel fibers mimicking the in vivo environment, we conducted accelerated stability tests. SiO2-coated PVA hydrogel fibers showed improved stability over a one-week incubation period under a harsh environment, preventing swelling and preserving their mechanical and optical properties compared to uncoated fibers. These SiO2-coated PVA hydrogel fibers demonstrated nanoscale polymeric crystalline domains (6.5 ± 0.1 nm), an elastic modulus of 73.7 ± 31.7 MPa, a maximum elongation of 113.6 ± 24.2%, and minimal light transmission loss (1.9 ± 0.2 dB cm-1). Lastly, we applied these SiO2-coated PVA hydrogel fibers in vivo to optically activate the motor cortex of transgenic Thy1::ChR2 mice during locomotor behavioral tests. This mouse cohort was genetically modified to express the light-sensitive ion channel, channelrhodopsin-2 (ChR2), and implanted with hydrogel fibers to deliver light to the motor cortex area (M2). Light stimulation via hydrogel fibers resulted in optogenetically modulated mouse locomotor behaviors, including increased contralateral rotation, mobility speeds, and travel distances.

Deep-learning-assisted theoretical insights into the compatibility of environment friendly insulation medium with metal surface of power equipment.

Exploring a new generation of eco-friendly gas insulation medium to replace greenhouse gas sulphur hexafluoride (SF6) in power industry is significant for reducing the greenhouse effect and building a low-carbon environment. The gas-solid compatibility of insulation gas with various electrical equipment is also of significance before practical applications. Herein, take a promising SF6 replacing gas trifluoromethyl sulfonyl fluoride (CF3SO2F) for example, one strategy to theoretically evaluate the gas-solid compatibility between insulation gas and the typical solid surfaces of common equipment was raised. Firstly, the active site where the CF3SO2F molecule is prone to interact with other compounds was identified. Secondly, the interaction strength and charge transfer between CF3SO2F and four typical solid surfaces of equipment were studied by first-principles calculations and further analysis was conducted, with SF6 as the control group. Then, the dynamic compatibility of CF3SO2F with solid surfaces was investigated by large-scale molecular dynamics simulations with the aid of deep learning. The results indicate that CF3SO2F has excellent compatibility similar to SF6, especially in the equipment whose contact surface is Cu, CuO, and Al2O3 due to their similar outermost orbital electronic structures. Besides, the dynamic compatibility with pure Al surfaces is poor. Finally, preliminary experimental verifications indicate the validity of the strategy.

High-Throughput Screening of Gas Sensor Materials for Decomposition Products of Eco-Friendly Insulation Medium by Machine Learning.

Nowadays, trifluoromethyl sulfonyl fluoride (CF3SO2F) has shown great potential to replace SF6 as an eco-friendly insulation medium in the power industry. In this work, an effective and low-cost design strategy toward ideal gas sensors for the decomposed gas products of CF3SO2F was proposed. The strategy achieved high-throughput screening from a large candidate space based on first-principle calculation and machine learning (ML). The candidate space is made up of different transition metal-embedded graphic carbon nitrides (TM/g-C3N4) owing to their high surface area and subtle electronic structure. Four main noteworthy decomposition gases of CF3SO2F, namely, CF4, SO2, SO2F2, and HF, as well as their initial stable structure on TM/g-C3N4 were determined. The best-performing ML model was established and implemented to predict the interaction strength between gas products and TM/g-C3N4, thus determining the promising gas-sensing materials for target gases with the requirements of interaction strength, recovery time, sensitivity, and selectivity. Further analysis guarantees their stability and reveals the origin of excellent properties as a gas sensor. The high-throughput strategy opens a new avenue of rational and low-cost design principles of desirable gas-sensing materials in an interdisciplinary view.

A Study on Dual-Response Composite Hydrogels Based on Oriented Nanocellulose.

In nature, many biological tissues are composed of oriented structures, which endow tissues with special properties and functions. Although traditional hydrogels can achieve a high level of biomimetic composition, the orderly arrangement of internal structures remains a challenge. Therefore, it is of great significance to synthesize hydrogels with oriented structures easily and quickly. In this study, we first proposed and demonstrated a fabrication process for producing a well-ordered and dual-responsive cellulose nanofibers + hyaluronic acid methacrylate (CN+HAMA) hydrogels through an extrusion-based three-dimensional (3D) printing process. CN in the CN+HAMA hydrogels are directionally aligned after extrusion due to shear stress. In addition, the synthesized hydrogels exhibited responsive behaviors to both temperature and ultraviolet light. Since the temperature-responsiveness is reversible, the hydrogels can transit between the gelation and solution states while retaining their original qualities. Furthermore, the developed well-oriented CN+HAMA hydrogels induced directional cell growth, paving the way for potential applications in ordered biological soft-tissue repair.

Discovery of 2,5-diphenyl-1,3,4-thiadiazole derivatives as HDAC inhibitors with DNA binding affinity.

Incorporating a DNA-binding fragment in HDAC inhibitors has been proved to be an effective strategy for the treatment of hematologic malignancies by our group. However, similar to other approved HDAC inhibitors, their effects on solid tumor were poor. For this issue, a series of 2,5-diphenyl-1,3,4-thiadiazole hydroxamate derivatives were designed and synthesized as the HDAC inhibitors with DNA binding affinity. Among the target compounds, 4j not only bound with DNA effectively but also exhibited the most potent inhibitory activity against HDAC1 with the IC50 of 15 nM. Compared to SAHA, compound 4j displayed stronger antiproliferative activity in tested tumor cell lines. Western blot analysis showed that 4j could enhance the acetylation of histone H3 and α-tubulin, as well as promote the activation of caspase 3 in HCT116 and MC38 cell lines. Furthermore, these responses resulted in significant suppression of tumor growth in the MC38 tumor model. This work validated that compound 4j was a promising lead compound for further structural optimization.

Fluid-driven hydrogel actuators with an origami structure.

Owing to the innate good biocompatibility, tissue-like softness and other unique properties, hydrogels are of particular interest as promising compliant materials for biomimetic soft actuators. However, the actuation diversity of hydrogel actuators is always restricted by their structure design and fabrication methods. Herein, origami structures were introduced to the design of fluid-driven hydrogel actuators to achieve diverse actuation movements, and a facile fabrication strategy based on removable templates and inside-out diffusion-induced in situ hydrogel crosslinking was adopted. As a result, three types of modular cuboid actuator units (CAUs) achieved linear motion, bending, and twisting. Moreover, combinations of multiple CAUs achieved different actuation modes, including actuation decoupling, superposition, and reprogramming. The diverse actuation functionality would enable new possibilities in application fields for hydrogel soft actuators. Several simple application demos, such as grippers for grasping tasks and a multi-way circuit switch, demonstrated their potential for further applications.

A methacrylated hyaluronic acid network reinforced Pluronic F-127 gel for treatment of bacterial keratitis.

In this study, we developed a novelin situthermoresponsive gel by introducing crosslinked methacrylated hyaluronic acid (HA-MA) networks into Pluronic F-127 (PF-127) gel (HP gel) to achieve sustained levofloxacin (LFX) delivery in bacterial keratitis treatment. The interactions between PF-127 molecules and HA-MA networks were studied by scanning electron microscopy, rheology, dynamic light scattering, differential scanning calorimetry, and small angle x-ray scattering. The results showed that the HP gel exhibited a higher critical gelling temperature and lower viscosity than the PF-127 gel (P gel), and could form a uniform thin layer on the ocular surface. Moreover, the drug release profile and gel dissolution rate revealed that the HA-MA network could retard the diffusion and dissolution of drug molecules and prolong the drug release time, which corresponded to an enhanced antibacterial ability of the HP-LFX gel. Furthermore, the HP gel exhibited low cytotoxicity to human corneal epithelial cells. Finally, anin vivopharmacodynamic study was conducted with rabbit keratitis models. An improved treatment efficacy was observed after application of the HP-LFX gels. This study highlights the potential of HP gels in ophthalmic drug delivery.

An Integrated Centrifugal Degassed PDMS-Based Microfluidic Device for Serial Dilution.

We propose an integrated serial dilution generator utilizing centrifugal force with a degassed polydimethylsiloxane (PDMS) microfluidic device. Using gas-soluble PDMS as a centrifugal microfluidic device material, the sample can be dragged in any arbitrary direction using vacuum-driven force, as opposed to in a single direction, without adding further actuation components. The vacuum-driven force allows the device to avoid the formation of air bubbles and exhibit high tolerance in the surface condition. The device was then used for sample metering and sample transferring. In addition, centrifugal force was used for sample loading and sample mixing. In this study, a series of ten-fold serial dilutions ranging from 100 to 10-4 with about 8 µL in each chamber was achieved, while the serial dilution ratio and chamber volume could easily be altered by changing the geometrical designs of the device. As a proof of concept of our hybrid approach with the centrifugal and vacuum-driven forces, ten-fold serial dilutions of a cDNA (complementary DNA) sample were prepared using the device. Then, the diluted samples were collected by fine needles and subject to a quantitative polymerase chain reaction (qPCR), and the results were found to be in good agreement with those for samples prepared by manual pipetting.

Passive micropumping in microfluidics for point-of-care testing.

Suitable micropumping methods for flow control represent a major technical hurdle in the development of microfluidic systems for point-of-care testing (POCT). Passive micropumping for point-of-care microfluidic systems provides a promising solution to such challenges, in particular, passive micropumping based on capillary force and air transfer based on the air solubility and air permeability of specific materials. There have been numerous developments and applications of micropumping techniques that are relevant to the use in POCT. Compared with active pumping methods such as syringe pumps or pressure pumps, where the flow rate can be well-tuned independent of the design of the microfluidic devices or the property of the liquids, most passive micropumping methods still suffer flow-control problems. For example, the flow rate may be set once the device has been made, and the properties of liquids may affect the flow rate. However, the advantages of passive micropumping, which include simplicity, ease of use, and low cost, make it the best choice for POCT. Here, we present a systematic review of different types of passive micropumping that are suitable for POCT, alongside existing applications based on passive micropumping. Future trends in passive micropumping are also discussed.

A Compact, Syringe-Assisted, Vacuum-Driven Micropumping Device.

In this paper, a simple syringe­assisted pumping method is introduced. The proposed fluidic micropumping system can be used instead of a conventional pumping system which tends to be large, bulky, and expensive. The micropump was designed separately from the microfluidic channels and directly bonded to the outlet of the microfluidic device. The pump components were composed of a dead­end channel which was surrounded by a microchamber. A syringe was then connected to the pump structure by a short tube, and the syringe plunger was manually pulled out to generate low pressure inside the microchamber. Once the sample was loaded in the inlet, air inside the channel diffused into the microchamber through the PDMS (polydimethylsiloxane) wall, acting as a dragging force and pulling the sample toward the outlet. A constant flow with a rate that ranged from 0.8 nl · s - 1 to 7.5 nl · s - 1 was achieved as a function of the geometry of the pump, i.e., the PDMS wall thickness and the diffusion area. As a proof-of-concept, microfluidic mixing was demonstrated without backflow. This method enables pumping for point-of-care testing (POCT) with greater flexibility in hand-held PDMS microfluidic devices.

A robust, portable and backflow-free micromixing device based on both capillary- and vacuum-driven flows.

In capillary- or vacuum-driven microfluidics, surge backflow events are common when merging or pumping two similar or dissimilar liquids together if a pressure difference exists between them. In this work, a robust, portable micromixing device that is insensitive to backflow was designed, fabricated and characterised. A capillary-driven pressure balancing bypass connected between two inlet ports diminished the initial pressure difference caused by capillarity and gravity present in each liquid at the two inlet ports. Then, using manual syringe-assisted vacuum-driven pumping that operated based on the high gas permeability of polydimethylsiloxane, the two pre-balanced liquid streams could synchronously enter a dead-end micromixing channel without any backflow. To test the performance of this device, we first used it to mix two aqueous solutions of different coloured dyes. We varied the initial volume difference between the solutions to study the effect of gravity-induced pressure difference on mixing. Next, as a proof-of-concept application, ABO/Rh blood groups were successfully determined through detection of blood antigen-antibody agglutination. The filling time of agglutinated samples, driven by the simple syringe-assisted pumping, in the dead-end mixing channel was consistently 10% longer than that of blood samples without the agglutination reaction. Thus, the proposed device shows great potential for use in a wide variety of blood typing assays, agglutination-based assays and point-of-care or lab-on-a-chip testing applications.

Introduction of a Chemical-Free Metal PDMS Thermal Bonding for Fabrication of Flexible Electrode by Metal Transfer onto PDMS.

Polydimethylsiloxane (PDMS) is a flexible and biocompatible material widely used in the fabrication of microfluidic devices, and is often studied for the fabrication of flexible electrodes. The most popular method of fabricating a flexible electrode using PDMS is done by transferring a metal electrode onto said PDMS. However, the transfer process is difficult and the transferred metal layer is easily damaged due to inherently weak adhesion forces between the metal and PDMS, thus requiring a chemical treatment or sacrificial layer between the two. The fabrication process using a chemical treatment or sacrificial layer is complicated and expensive, which is the major limitation of using PDMS in the fabrication of flexible electrodes. This paper discusses the findings of a possible solution to create strong bonding between PDMS and various metals (copper, nickel and silver) using a chemical-free metal to PDMS thermal bonding technique. This method is the same as the PDMS curing process, but with a variation in the curing condition. The condition required to create strong bonding was studied by observing copper transferred by various PDMS curing conditions, including the standard condition. The condition creating the strong bonding was baking PDMS (5:1 = base polymer: curing agent) at 150 °C for 20 min. Experimentation showed that the optimum thickness of the transferred metal shows that the optimum thickness is approximately 500 nm, which allows for a higher resistance to stresses. The successful transfer of copper, nickel and silver layers onto PDMS with a stronger adhesion force opens up many new applications dealing with the fabrication of flexible electrodes, sensors, and flexible soft magnets.