Reagentless protein-based electrochemical biosensors.

The creation of reagentless protein-based biosensors that are capable of monitoring molecular analytes directly in bodily fluids could revolutionize our understanding of biology and personalized health monitoring. The limited number of molecular sensors that are currently available in the market depends on the specific enzymatic or chemical reactivity of their target analytes and therefore are not applicable to many relevant biomarkers. Aiming to overcome this limited molecular sensing generality, a new class of reagentless protein-based electrochemical sensors has been introduced for the direct measurements of biomarkers in unprocessed biological fluids. This mini-review will discuss the most recent cutting-edge discoveries for the development of electroanalytical modular biosensors, where all the sensors' components are integrated into a self-sufficient sensor allowing hence its autonomous functionality.

Enhancing the photoluminescence and cellular uptake of fluorescent carbon nanodots via cubosome lipid nanocarriers.

Carbon nanodots (C-dots) have attracted much attention for their use in the fields of bioimaging, drug delivery, and sensing due to their excellent fluorescent and photoluminescent properties, photostability, biocompatibility, and amenability to surface modification. Herein, we report a nanocomposite formulation of C-dots (<5 nm) encapsulated in lipid-based lyotropic liquid crystalline nanoparticles (∼250 nm) via either passive diffusion or electrostatic mechanisms. The physicochemical properties of the nanocomposite formulation including particle size, surface charge, internal cubic nanostructures, and pH-dependent fluorescent properties were characterised. Upon loading of C-dots into lipid nanoparticles, the highly ordered inverse bicontinuous cubic mesophase existed in the internal phase of the nanoparticles, demonstrated by synchrotron small angle X-ray scattering, molecular dynamic simulation and cryogenic transmission electron microscopy. The pH-dependent fluorescent property of the C-dots was modified via electrostatic interaction between the C-dots and cationic lipid nanoparticles, which further enhanced the brightness of C-dots through self-quenching prevention. The cytotoxicity and cellular uptake efficiency of the developed nanocomposites were also examined in an epithelial gastric adenocarcinoma cell line (AGS) and a macrophage cell line (stimulated THP-1). Compared to free C-dots, the uptake and cell imaging potential of the C-dot nanocomposites was significantly improved, by several orders of magnitude as demonstrated by cytoplasmic fluorescent intensities using confocal microscopy. Loading C-dots into mesoporous lipid nanocarriers presents a new way of modifying C-dot physicochemical and fluorescent properties, alternative to direct chemical surface modification, and advances the bioimaging potential of C-dots by enhancing cellular uptake efficiency and converging C-dot light emission.

3D-printed solar evaporator with seashell ornamentation-inspired structure for zero liquid discharge desalination.

Solar-driven interfacial evaporation has enormous promise for fresh water recovery and salt harvesting, but salt accumulation-related challenges stand in its way. Herein, we report a spined groove-ridge pairs inspired by the shell ornamentation of the Vasticardium vertebratum, which addresses salt accumulation by artfully integrating salt reflux into localized salt crystallization. The seashell-mimetic radial V-groove array enables the 3D evaporator to transport water rapidly and directionally, resulting in high-performance water evaporation (∼95% efficiency) and localized crystallization. The periodic spines enlightened by the spine-bearing ridge on the seashell provide considerable micro-unit salt reflux. The 2-in-1 integration design endows the three-dimensional evaporator with superior solar-driven zero liquid discharge and excellent long-term salt resistance even when dealing with high-salinity brine (20 wt% NaCl) and a series of heavy metallic salt solutions. Our design offers a new alternative solution to avoiding salt scaling and could advance locally crystallized solar evaporators towards practical applications.

Self-assembly of carbon nanodots induced by liquid-liquid phase separation in a surface microdroplet.

Evaporating a sessile drop of ternary solutions containing one hydrotrope (such as ethanol) and two immiscible fluids exhibiting fascinating phase separation behaviours, has opened up a new pathway for controlled nanomaterial assembly. In this work, we studied the influence of liquid-liquid phase separation (LLPS) on the assembly of carbon nanodots (C-dots), 2 nm fluorescent carbon-based nanomaterials with high water solubility. Through self-evaporation of a micro-sized droplet containing ethanol, C-dot-water solution and different oils on a hydrophobic surface, C-dots rearranged into film, porous and granular structures by controlling the properties of oil component in the tenary droplet. Vapour pressure, solubility, surface tension and compositions of the oil components were investigated systematically for their impacts on the evaporation process of C-dot-laden droplets. By using confocal microscopy, we clearly revealed that C-dot assembly was triggered by LLPS in these four oil-water-ethanol ternary systems. The corresponding evaporation and assembly processes were unravelled to be determined by how the ternary solutions pass through the liquid-liquid equilibrium curves in the phase diagrams during evaporation. Our findings deepen the understanding of phase-separation behaviours for nanomaterial assembly as well as provide a novel, simple, and well-controlled approach for depositing different C-dot based nanostructures onto surfaces, which will benefit a wide range of practical applications in the fields of energy, environment and health.

Effects of Leader-Follower Extraversion Congruence and Sectoral Difference on Leader-Member Exchange: A Cross-Sectional Study.

PURPOSE: Drawing upon self-categorization theory and the comparative literature on public and private sectors, the purpose of this study is to examine whether leader-follower extraversion congruence is positively related to leader-member exchange (LMX) and whether congruence at high levels of extraversion results in higher LMX than congruence at low levels. Furthermore, the study aims to investigate the moderating role of sectoral difference in the relationship between extraversion fit and LMX. METHODS: Participants were 320 leader-follower dyads (53 leaders and 320 followers) from various public and private sectors in the Chinese cultural context. The extraversion part of the Revised NEO Personality Inventory (NEO-PI-R) and leader-member exchange multidimensional measure (LMX-MDM) were used to measure extraversion and LMX, respectively. Hypotheses were tested using cross-level moderated polynomial regression and response surface analysis. RESULTS: Leader-follower extraversion congruence was not significantly associated with LMX, and there was no significant difference in LMX between congruence at high levels of extraversion and congruence at low levels. However, sectoral difference moderated the relationship between extraversion fit and LMX. Specifically, in the public sector, leader-follower extraversion congruence was positively related to LMX, and LMX was higher when leader and follower extraversion were both at a high level compared to when they were at a low level. In the private sector, this fit effect vanished. PRACTICAL IMPLICATIONS: The results suggest that, in the public sector, when organizations deal with the deployment of staff, taking leader-follower extraversion fit into account may mitigate possible later relationship conflicts. However, in the private sector, by not emphasizing extraversion fit, organizations can focus resources on more crucial factors. ORIGINALITY/VALUE: By considering sectoral difference as the boundary condition of leader-follower extraversion fit, this study extends the comparative literature on public and private sectors and supports self-categorization theory.

Paper-based analytical device for high-throughput monitoring tetracycline residue in milk.

A low-cost and portable paper-based analytical device has been developed for high throughput and on-site monitoring TC residue in milk through visualized colorimetric reaction. The filtration and concentration effect induced by the porous nature of paper contribute to strengthen the color intensity, leading to quantitative and sensitive detection of tetracycline reaching 1 ppm detection limit, with the linear range of 1-100 ppm both in water and milk samples. The applicability was demonstrated by detection of TC in 18 different types of real milk samples with good recovery ranging from 88% to 113%. Furthermore, the dynamic degradation behavior of tetracycline was monitored through the device. To the best of our knowledge, this is the first report of colorimetric detection of tetracycline in milk using the paper-based device. This simple, fast, cost-effective (~$0.50 per device) and equipment-free paper-based platform provides a promising tool for future application in food and environmental safety.

Encapsulated Nanodroplets for Enhanced Fluorescence Detection by Nano-Extraction.

Enhancement of the detection signal of fluorescence microscopy in highly diluted solutions is of great importance in chemical analysis, sensing, and bioassay applications. Surface nanodroplets with atto- to femto-liter volumes are promising tools for sensitive online detection by integrating their extremely efficient nano-extraction and optical advantages. In this paper, the development of novel basic units of nanodroplets-in-a-microdroplet by simple solvent exchange is reported. The encapsulated nanodroplets are applied for ultrasensitive and online detection in fluorescence imaging. The biphasic nature of the droplet composite enables simultaneous extraction and enrichment of both hydrophobic and hydrophilic compounds. Furthermore, the desirable lensing effect of the curved surface of the nanodroplets enhances the collection of light emitted from the fluorophore extracted in the droplets by ≈60-fold, allowing sensitive and quantitative analysis of the fluorophore using fluorescence microscopy. The results highlight the potential of encapsulated nanodroplets as a simple and innovative method of signal enhancement in chemical analysis. By integrating selective concentration, extraction, and sensitive detection, the encapsulated nanodroplets reported here may have broad applications in many chemical and biological matrices.

Integrated Nanoextraction and Colorimetric Reactions in Surface Nanodroplets for Combinative Analysis.

A combinative approach for chemical analysis makes it possible to distinguish a mixture of a large number of compounds from other mixtures in a single step. This work demonstrates a combinative analysis approach using surface nanodroplets for integrating nanoextraction and colorimetric reactions for the identification of multicomponent mixtures. The model analytes are acidic compounds dissolved in an oil that are extracted into aqueous droplets on a solid substrate. The proton from acid dissociation reacts with the halochromic chemical compounds inside the droplets, leading to the color change of the droplets. The rate of the colorimetric reaction exhibits certain specificity for the acid type, distinguishing acid mixtures with the same pH value. The underlying principle is that the acid transport rate is associated with the partition coefficient and the dissociation constant of the acid, as well as to the concentration in the oil. As a demonstration, we showed that droplet-based combinative analysis can be applied for anti-counterfeiting of various alcoholic spirits by comparing the decoloration time of organic acid mixtures in the spirits. The readout can be done by a common hand-hold mobile phone.

Nanochitin/metal ion dual reinforcement in synthetic polyacrylamide network-based nanocomposite hydrogels.

Nanocomposite hydrogels consisting of a synthetic matrix reinforced by nanosized crystalline polysaccharides offer significant potential in various fields. Different from nanocellulose, the combination of nanochitin with synthetic polymers to obtain nanocomposite hydrogels has not been extensively and systematically studied. Herein, a physically and chemically dual crosslinked nanocomposite hydrogel was successfully synthesized, where chitin nanowhiskers (ChNWs) and Zn2+ were incorporated within polyacrylamide (PAAm) matrix. Nanochitin/metal ion dual reinforcement imparts increased elasticity, enhanced mechanical properties, and improved recovery performance to PAAm network. The PAAm/ChNWs/Zn2+ hydrogel could be stretched to over 13 times its original length with tensile strength of 321.9 ±â€¯8.2 kPa, and restore its original shape rapidly even when compressed at a strain of 95% with a corresponding compressive strength of 6.95 ±â€¯0.20 MPa. The multiple crosslinks and interactions among ChNWs, Zn2+ and synthetic polymeric network were investigated. Moreover, the hydrogel was applied in drug release and soft bioelectronics.

Portable paper sensors for the detection of heavy metals based on light transmission-improved quantification of colorimetric assays.

An accurate quantification method with a wide linearity range is paramount for the development of low-cost, portable and point-of-care sensors. This work reports a new approach to analyze the colorimetric assays on paper-based sensors using the quantification from a light transmission method. Compared to the commonly-developed color intensity measurement on scanned digital images, a portable transmission densitometer is capable of directly quantifying the optical density of colorimetric results. The detection of heavy metals in an aqueous system, including Fe(ii), Cu(ii), and Ni(ii), was carried out to demonstrate the good performance and reliability of this method. Our measurements show that the linear quantification range spans from 0.5-500 mg L-1 for the assays of Cu(ii) and Fe(ii) and from 2-500 mg L-1 for Ni(ii) based on the reading of transmitted light through the assay spot. As a comparison, the linear range is restricted to 0.5-50 mg L-1 for the same assays when analysed by the common reflection method, suggesting a significant improvement in the accuracy and sensitivity of high analyte concentrations from the light transmission method. By expanding the linearity range, this method further streamlines the sampling procedure during analysis and will greatly advance the future development of paper-based analytical sensors.

Automated Femtoliter Droplet-Based Determination of Oil-Water Partition Coefficient.

The oil-water partition coefficient of organic compounds is an essential parameter for the determination of their behaviors in environments, food, drug delivery, and biomedical systems, just to name a few. In this work, we establish a highly efficient approach to quantify the partition/distribution coefficient using surface femtoliter droplets. In our approach, droplets of 1-octanol were produced on the surface of a solid substrate in contact with the flow of an aqueous solution of the analyte. The analyte was rapidly enriched in the droplets from the flow and reached the partition equilibrium in a few seconds. The entire procedure was automated by continuous solvent exchange, and the analyte partition in the droplets was quantified from the in situ UV-vis spectrum collected by a microspectrophotometer. Our approach was validated for several substances with the octanol-water partition/distribution coefficient ranging from -1.5 to 4, where our results were in good agreement with the values reported in the literature. This method took ∼3 min to detect one analyte with the volume of the organic solvent at ∼50 µL. Thus, our surface droplet platform can greatly minimize the consumption of both solvent and analytes and can shorten the time for the determination of the partition of new compounds, which overcomes the drawbacks of the traditional shake-flask method and presents excellent reproducibility, high accuracy, cost-effectiveness, and labor-saving operation. The highly efficient micro/nanoextraction, partition, and real-time detection enabled by the surface droplets has the potential for many other high-throughput applications.

How Leaders' Psychological Capital Influence Their Followers' Psychological Capital: Social Exchange or Emotional Contagion.

Using a sample of 32 work teams (32 work team leaders and their 321 followers) in Chinese cultural context, this study investigated the relationships between leaders' and their followers' psychological capital and the multilevel multiple mediation effects of social exchange and emotional contagion. PsyCap questionnaire (PCQ), leader-member exchange scale, and the positive affect scale in the positive and negative affect scale (PANAS) were adopted to measure variables. A total of 430 questionnaires were distributed in 2014 and the response rates were 90.2%. Structural equation model and hierarchical linear model were applied to analyze the survey data. The results revealed that leaders' psychological capital had a positive influence on their followers' psychological capital. Leader-member exchange was the cross-level mediator between leaders' psychological capital and their followers'. The cross-level mediating effect of leaders' positive emotions perceived by followers was not significant. The results of this study extended the social exchange theory and enriched researches on leadership. The implication was discussed in details.

Controlled addition of new liquid component into surface droplet arrays by solvent exchange.

HYPOTHESIS: Microscopic droplets integrating multiple functionalities are essential in the microcompartmentalized related reaction and applications. Solvent exchange is a simple approach for producing femtoliter surface droplets by the transit oversaturation created at the mixing front of a solution by a poor solvent. But it remains challenging to control the compositions in nanodroplets. Our hypothesis is the new liquid component can be added to the pre-formed surface droplets at certain ratios controlled by solvent exchange. EXPERIMENTS: In this work we investigate the growth of the droplets during addition of a new component by solvent exchange. Two-component droplets were formed on a microdomain patterned substrate as highly ordered arrays. The physical and chemical parameters that control droplet composition and a possible application of the binary droplet arrays were presented in this work. FINDINGS: The added amount of the second component in the binary droplet can be quantitatively controlled by the solution and flow conditions. The theoretical prediction of the component ratio based on the droplet diffusive growth dynamics mode shows a good agreement with the experimental results. The results show that the solvent exchange on the surface with pre-formed droplets provides a highly efficient method to tune the droplet compositions to desired ratio. The unique feature of this approach enables a gradient structure of droplet composition over the surface, demonstrated by an application of different microlens performance on a surface.

Barrier-free patterned paper sensors for multiplexed heavy metal detection.

Patterned paper sensors such as letter- and barcode-shaped sensors have become a subject of growing interest due to the potential in information embedding and data interpretation, which brings a requirement on easily fabricating these paper-based analytical devices. The answer, in part, may lie in the influence of paper structure on the performance of paper-based analytical devices. After investigating the effect of physical properties of paper on precipitation and non-precipitation assays for detecting Fe(II), here we propose a simple and promising approach for barrier-free paper patterning. Without building hydrophobic boundaries, the precipitates of sensing reactions on low-bulk and medium-thick paper substrates allow patterned signal readout directly. As a proof of concept, barrier-free patterned paper sensors for detecting heavy metals were fabricated, with detection limits of 0.25 ppm for Fe(II), 0.4 ppm for Ni(II), and 0.5 ppm for Cu(II). Our work provides a valuable perspective on fabrication of patterned paper sensors.

Functional Femtoliter Droplets for Ultrafast Nanoextraction and Supersensitive Online Microanalysis.

A universal femtoliter surface droplet-based platform for direct quantification of trace of hydrophobic compounds in aqueous solutions is presented. Formation and functionalization of femtoliter droplets, concentrating the analyte in the solution, are integrated into a simple fluidic chamber, taking advantage of the long-term stability, large surface-to-volume ratio, and tunable chemical composition of these droplets. In situ quantification of the extracted analytes is achieved by surface-enhanced Raman scattering (SERS) spectroscopy by nanoparticles on the functionalized droplets. Optimized extraction efficiency and SERS enhancement by tuning droplet composition enable quantitative determination of hydrophobic model compounds of rhodamine 6G, methylene blue, and malachite green with the detection limit of 10-9 to 10-11 m and a large linear range of SERS signal from 10-9 to 10-6 m of the analytes. The approach addresses the current challenges of reproducibility and the lifetime of the substrate in SERS measurements. This novel surface droplet platform combines liquid-liquid extraction and highly sensitive and reproducible SERS detection, providing a promising technique in current chemical analysis related to environment monitoring, biomedical diagnosis, and national security monitoring.

Crystallization of Femtoliter Surface Droplet Arrays Revealed by Synchrotron Small-Angle X-ray Scattering.

The crystallization of oil droplets is critical in the processing and storage of lipid-based food and pharmaceutical products. Arrays of femtoliter droplets on a surface offer a unique opportunity to study surfactant-free colloidlike systems. In this work, the crystal growth process in these confined droplets was followed by cooling a model lipid (trimyristin) from a liquid state utilizing synchrotron small-angle X-ray scattering (SAXS). The measurements by SAXS demonstrated a reduced crystallization rate and a greater degree of supercooling required to trigger lipid crystallization in droplets compared to those of bulk lipids. These results suggest that surface droplets crystallize in a stochastic manner. Interestingly, the crystallization rate is slower for larger femtoliter droplets, which may be explained by the onset of crystallization from the three-phase contact line. The larger surface nanodroplets exhibit a smaller ratio of droplet volume to the length of three-phase contact line and hence a slower crystallization rate.

"Periodic-table-style" paper device for monitoring heavy metals in water.

If a paper-based analytical device (µ-PAD) could be made by printing indicators for detection of heavy metals in chemical symbols of the metals in a style of the periodic table of elements, it could be possible for such µ-PAD to report the presence and the safety level of heavy metal ions in water simultaneously and by text message. This device would be able to provide easy solutions to field-based monitoring of heavy metals in industrial wastewater discharges and in irrigating and drinking water. Text-reporting could promptly inform even nonprofessional users of the water quality. This work presents a proof of concept study of this idea. Cu(II), Ni(II), and Cr(VI) were chosen to demonstrate the feasibility, specificity, and reliability of paper-based text-reporting devices for monitoring heavy metals in water.

Understanding thread properties for red blood cell antigen assays: weak ABO blood typing.

"Thread-based microfluidics" research has so far focused on utilizing and manipulating the wicking properties of threads to form controllable microfluidic channels. In this study we aim to understand the separation properties of threads, which are important to their microfluidic detection applications for blood analysis. Confocal microscopy was utilized to investigate the effect of the microscale surface morphologies of fibers on the thread's separation efficiency of red blood cells. We demonstrated the remarkably different separation properties of threads made using silk and cotton fibers. Thread separation properties dominate the clarity of blood typing assays of the ABO groups and some of their weak subgroups (Ax and A3). The microfluidic thread-based analytical devices (µTADs) designed in this work were used to accurately type different blood samples, including 89 normal ABO and 6 weak A subgroups. By selecting thread with the right surface morphology, we were able to build µTADs capable of providing rapid and accurate typing of the weak blood groups with high clarity.

Barcode-like paper sensor for smartphone diagnostics: an application of blood typing.

This study introduced a barcode-like design into a paper-based blood typing device by integrating with smartphone-based technology. The concept of presenting a paper-based blood typing assay in a barcode-like pattern significantly enhanced the adaptability of the assay to the smartphone technology. The fabrication of this device involved the use of a printing technique to define hydrophilic bar channels which were, respectively, treated with Anti-A, -B, and -D antibodies. These channels were then used to perform blood typing assays by introducing a blood sample. Blood type can be visually identified from eluting lengths in bar channels. A smartphone-based analytical application was designed to read the bar channels, analogous to scanning a barcode, interpret this information, and then report results to users. The proposed paper-based blood typing device is rapidly read by smartphones and easy for the user to operate. We envisage that the adaptation of paper-based devices to the widely accepted smartphone technology will increase the capability of paper-based diagnostics with rapid assay result interpretation, data storage, and transmission.

Paper-based device for rapid typing of secondary human blood groups.

We report the use of bioactive paper for typing of secondary human blood groups. Our recent work on using bioactive paper for human blood typing has led to the discovery of a new method for identifying haemagglutination of red blood cells. The primary human blood groups, i.e., ABO and RhD groups, have been successfully typed with this method. Clinically, however, many secondary blood groups can also cause fatal blood transfusion accidents, despite the fact that the haemagglutination reactions of secondary blood groups are generally weaker than those of the primary blood groups. We describe the design of a user-friendly sensor for rapid typing of secondary blood groups using bioactive paper. We also present mechanistic insights into interactions between secondary blood group antibodies and red blood cells obtained using confocal microscopy. Haemagglutination patterns under different conditions are revealed for optimization of the assay conditions.