PACMan: A software package for automated single-cell chlorophyll fluorometry.

Microalgae, small photosynthetic unicells, are of great interest to ecology, ecotoxicology and biotechnology and there is a growing need to investigate the ability of cells to photosynthesize under variable conditions. Current strategies involve hand-operated pulse-amplitude-modulated (PAM) chlorophyll fluorimeters, which can provide detailed insights into the photophysiology of entire populations- or individual cells of microalgae but are typically limited in their throughput. To increase the throughput of a commercially available MICROSCOPY-PAM system, we present the PAM Automation Control Manager ('PACMan'), an open-source Python software package that automates image acquisition, microscopy stage control and the triggering of external hardware components. PACMan comes with a user-friendly graphical user interface and is released together with a stand-alone tool (PAMalysis) for the automated calculation of per-cell maximum quantum efficiencies (= Fv /Fm ). Using these two software packages, we successfully tracked the photophysiology of >1000 individual cells of green algae (Chlamydomonas reinhardtii) and dinoflagellates (genus Symbiodiniaceae) within custom-made microfluidic devices. Compared to the manual operation of MICROSCOPY-PAM systems, this represents a 10-fold increase in throughput. During experiments, PACMan coordinated the movement of the microscope stage and triggered the MICROSCOPY-PAM system to repeatedly capture high-quality image data across multiple positions. Finally, we analyzed single-cell Fv /Fm with the manufacturer-supplied software and PAMalysis, demonstrating a median difference <0.5% between both methods. We foresee that PACMan, and its auxiliary software package will help increase the experimental throughput in a range of microalgae studies currently relying on hand-operated MICROSCOPY-PAM technologies.

Critical Role of Functional Groups Containing N, S, and O on Graphene Surface for Stable and Fast Charging Li-S Batteries.

Lithium-sulfur (Li-S) batteries are considered one of the most promising energy storage technologies, possibly replacing the state-of-the-art lithium-ion (Li-ion) batteries owing to their high energy density, low cost, and eco-compatibility. However, the migration of high-order lithium polysulfides (LiPs) to the lithium surface and the sluggish electrochemical kinetics pose challenges to their commercialization. The interactions between the cathode and LiPs can be enhanced by the doping of the carbon host with heteroatoms, however with relatively low doping content (<10%) in the bulk of the carbon, which can hardly interact with LiPs at the host surface. In this study, the grafting of versatile functional groups with designable properties (e.g., catalytic effects) directly on the surface of the carbon host is proposed to enhance interactions with LiPs. As model systems, benzene groups containing N/O and S/O atoms are vertically grafted and uniformly distributed on the surface of expanded reduced graphene oxide, fostering a stable interface between the cathode and LiPs. The combination of experiments and density functional theory calculations demonstrate improvements in chemical interactions between graphene and LiPs, with an enhancement in the electrochemical kinetics, power, and energy densities.

The Combination of 2D Layered Graphene Oxide and 3D Porous Cellulose Heterogeneous Membranes for Nanofluidic Osmotic Power Generation.

Salinity gradient energy, as a type of blue energy, is a promising sustainable energy source. Its energy conversion efficiency is significantly determined by the selective membranes. Recently, nanofluidic membrane made by two-dimensional (2D) nanomaterials (e.g., graphene) with densely packed nanochannels has been considered as a high-efficient membrane in the osmotic power generation research field. Herein, the graphene oxide-cellulose acetate (GO-CA) heterogeneous membrane was assembled by combining a porous CA membrane and a layered GO membrane; the combination of 2D nanochannels and 3D porous structures make it show high surface-charge-governed property and excellent ion transport stability, resulting in an efficient osmotic power harvesting. A power density of about 0.13 W/m2 is achieved for the sea-river mimicking system and up to 0.55 W/m2 at a 500-fold salinity gradient. With different functions, the CA and GO membranes served as ion storage layer and ion selection layer, respectively. The GO-CA heterogeneous membrane open a promising avenue for fabrication of porous and layered platform for wide potential applications, such as sustainable power generation, water purification, and seawater desalination.

Studies of Emission Processes of Polymer Additives into Water Using Quartz Crystal Microbalance-A Case Study on Organophosphate Esters.

Plastic materials contain various additives, which can be released during the entire lifespan of plastics and pose a threat to the environment and human health. Despite our knowledge on leakage of additives from products, accurate and rapid approaches to study emission kinetics are largely lacking, in particular, methodologies that can provide in-depth understanding of polymer/additive interactions. Here, we report on a novel approach using quartz crystal microbalance (QCM) to measure emissions of additives to water from polymer films spin-coated on quartz crystals. The methodology, being accurate and reproducible with a standard error of ±2.4%, was applied to a range of organophosphate esters (OPEs) and polymers with varying physicochemical properties. The release of most OPEs reached an apparent steady-state within 10 h. The release curves for the studied OPEs could be fitted using a Weibull model, which shows that the release is a two-phase process with an initial fast phase driven by partitioning of OPEs readily available at or close to the polymer film surface, and a slower phase dominated by diffusion in the polymer. The kinetics of the first emission phase was mainly correlated with the hydrophobicity of the OPEs, whereas the diffusion phase was weakly correlated with molecular size. The developed QCM-based method for assessing and studying release of organic chemicals from a polymeric matrix is well suited for rapid screening of additives in efforts to identify more sustainable replacement polymer additives with lower emission potential.

Tuning the morphologies of fluorine-doped tin oxides in the three-dimensional architecture of graphene for high-performance lithium-ion batteries.

The morphology of electrode materials plays an important role in determining the performance of lithium-ion batteries (LIBs). However, studies on determining the most favorable morphology for high-performance LIBs have rarely been reported. In this study, a series of F-doped SnO x (F-SnO2 and F-SnO) materials with various morphologies was synthesized using ethylenediamine as a structure-directing agent in a facile hydrothermal process. During the hydrothermal process, the F-SnO x was embedded in situ into the three-dimensional (3D) architecture of reduced graphene oxide (RGO) to form F-SnO x @RGO composites. The morphologies and nanostructures of F-SnO x , i.e., F-SnO2 nanocrystals, F-SnO nanosheets, and F-SnO2 aggregated particles, were fully characterized using electron microscopy, x-ray diffraction, and x-ray photoelectron spectroscopy. Electrochemical characterization indicated that the F-SnO2 nanocrystals uniformly distributed in the 3D RGO architecture exhibited higher specific capacity, better rate performance, and longer cycling stability than the F-SnO x with other morphologies. These excellent electrochemical performances were attributed to the uniform distribution of the F-SnO2 nanocrystals, which significantly alleviated the volume changes of the electrode material and shortened the Li ion diffusion path during lithiation/delithiation processes. The F-SnO2@RGO composite composed of uniformly distributed F-SnO2 nanocrystals also exhibited excellent rate performance, as the specific capacities were measured to be 1158 and 648 mA h g-1 at current densities of 0.1 and 5 A g-1, respectively.

Surface chemistry and structure manipulation of graphene-related materials to address the challenges of electrochemical energy storage.

Energy storage devices are important components in portable electronics, electric vehicles, and the electrical distribution grid. Batteries and supercapacitors have achieved great success as the spearhead of electrochemical energy storage devices, but need to be further developed in order to meet the ever-increasing energy demands, especially attaining higher power and energy density, and longer cycling life. Rational design of electrode materials plays a critical role in developing energy storage systems with higher performance. Graphene, the well-known 2D allotrope of carbon, with a unique structure and excellent properties has been considered a "magic" material with its high energy storage capability, which can not only aid in addressing the issues of the state-of-the-art lithium-ion batteries and supercapacitors, but also be crucial in the so-called post Li-ion battery era covering different technologies, e.g., sodium ion batteries, lithium-sulfur batteries, structural batteries, and hybrid supercapacitors. In this feature article, we provide a comprehensive overview of the strategies developed in our research to create graphene-based composite electrodes with better ionic conductivity, electron mobility, specific surface area, mechanical properties, and device performance than state-of-the-art electrodes. We summarize the strategies of structure manipulation and surface modification with specific focus on tackling the existing challenges in electrodes for batteries and supercapacitors by exploiting the unique properties of graphene-related materials.

Photophysiological response of Symbiodiniaceae single cells to temperature stress.

Photosynthetic dinoflagellates in the family Symbiodiniaceae engage in symbiosis with scleractinian corals. As coral 'bleaching' is partly governed by the thermal sensitivity of different Symbiodiniaceae lineages, numerous studies have investigated their temperature sensitivity. However, the systematic identification of single-cells with increased temperature resistance among these dinoflagellates has remained inaccessible, mostly due to a lack of technologies operating at the microscale. Here, we employed a unique combination of microfluidics, miniaturized temperature control, and chlorophyll fluorometry to characterize the single-cell heterogeneity among five representative species within the Symbiodiniaceae family under temperature stress. We monitored single-cell maximum quantum yields (Fv/Fm) of photosystem (PS) II under increasing temperature stress (22‒39 °C, + 1 °C every 15 min), and detected a significant Fv/Fm reduction at lineage-specific temperatures ranging from 28 °C to 34 °C alongside a 40- to 180- fold increase in intraspecific heterogeneity under elevated temperatures (>31 °C). We discovered that the initial Fv/Fm of a cell could predict the same cell's ability to perform PSII photochemistry under moderate temperature stress (<32 °C), suggesting its use as a proxy for measuring the thermal sensitivity among Symbiodiniaceae. In combination, our study highlights the heterogeneous thermal sensitivity among photosynthetic Symbiodiniaceae and adds critical resolution to our understanding of temperature-induced coral bleaching.

A microscopy-compatible temperature regulation system for single-cell phenotype analysis - demonstrated by thermoresponse mapping of microalgae.

This work describes a programmable heat-stage compatible with in situ microscopy for the accurate provision of spatiotemporally defined temperatures to different microfluidic devices. The heat-stage comprises an array of integrated thin-film Joule heaters and resistance temperature detectors (RTDs). External programming of the heat-stage is provided by a custom software program connected to temperature controllers and heater-sensor pairs. Biologically relevant (20-40 °C) temperature profiles can be supplied to cells within microfluidic devices as spatial gradients (0.5-1.5 °C mm-1) or in a time-varying approach via e.g. step-wise or sinusoidally varying profiles with negligible temperature over-shoot. Demonstration of the device is achieved by exposing two strains of the coral symbiont Symbiodinium to different temperature profiles while monitoring their single-cell photophysiology via chlorophyll fluorometry. This revealed that photophysiological responses to temperature depended on the exposure duration, exposure magnitude and strain background. Moreover, thermal dose analysis suggested that cell acclimatisation occurs under longer temperature (6 h) exposures but not under shorter temperature exposures (15 min). As the thermal sensitivity of Symbiodinium mediates the thermal tolerance in corals, our versatile technology now provides unique possibilities to research this interdependency at single cell resolution. Our results also show the potential of this heat-stage for further applications in fields such as biotechnology and ecotoxicology.

Core-Shell Structured Polyamide 66 Nanofibers with Enhanced Flame Retardancy.

We report the preparation of polymer nanofibers with enhanced flame retardancy by coaxial electrospinning polyamide 66 (PA 66) and nanoscale graphene hybridized with red phosphorus (NG-RP). Transmission electron microscopy and energy-dispersive X-ray spectroscopy revealed that the nanofibers contained a NG-RP-based core surrounded by a PA 66 shell. The flame-retardant characteristics of the nanofibers were investigated by thermal gravimetric analysis, micro combustion calorimetry, and a series of vertical flame tests. The encapsulation of the NG-RP not only enhanced the flame-retardant characteristics of the nanofibers, but also improved their mechanical properties while maintaining the color and luster of the polymer, making the resultant nanofibers appropriate for use in a wide range of applications.

Enhanced Photothermal Bactericidal Activity of the Reduced Graphene Oxide Modified by Cationic Water-Soluble Conjugated Polymer.

Surface modification of graphene is extremely important for applications. Here, we report a grafting-through method for grafting water-soluble polythiophenes onto reduced graphene oxide (RGO) sheets. As a result of tailoring of the side chains of the polythiophenes, the modified RGO sheets, that is, RGO-g-P3TOPA and RGO-g-P3TOPS, are positively and negatively charged, respectively. The grafted water-soluble polythiophenes provide the modified RGO sheets with good dispersibility in water and high photothermal conversion efficiencies (ca. 88%). Notably, the positively charged RGO-g-P3TOPA exhibits unprecedentedly excellent photothermal bactericidal activity, because the electrostatic attractions between RGO-g-P3TOPA and Escherichia coli (E. coli) bind them together, facilitating direct heat conduction through their interfaces: the minimum concentration of RGO-g-P3TOPA that kills 100% of E. coli is 2.5 µg mL-1, which is only 1/16th of that required for RGO-g-P3TOPS to exhibit a similar bactericidal activity. The direct heat conduction mechanism is supported by zeta-potential measurements and photothermal heating tests, in which the achieved temperature of the RGO-g-P3TOPA suspension (2.5 µg mL-1, 32 °C) that kills 100% of E. coli is found to be much lower than the thermoablation threshold of bacteria. Therefore, this research demonstrates a novel and superior method that combines photothermal heating effect and electrostatic attractions to efficiently kill bacteria.

Lightweight and Ultrastrong Polymer Foams with Unusually Superior Flame Retardancy.

High-performance flame-retardant materials are urgently needed to address outstanding issues that pertain to safety. Traditional flame retardants are toxic to the environment and/or lack the physical properties required for use in many contemporary applications. Here, we show that isocyanate-based polyimide (PI) foam, a flammable material, can exhibit unusually superior flame retardancy as well as other excellent properties, such as being lightweight and displaying high mechanical strength, by incorporating red phosphorus (RP)-hybridized graphene. The covalent bonds formed between the graphene platelets and the PI matrix provide the resultant PI foam with a specific Young's modulus (83 kNm kg-1) that is comparable to or even higher than those displayed by state-of-the-art foams, including silica aerogels, polystyrene foams, and polyurethane foams. In addition, even a low content of the RP-hybridized graphene (2.2 wt %) results in an exceptionally higher limiting oxygen index (39.4) than those of traditional flame-retardant polymer-based materials (typically 20-30). The resultant PI foam also exhibits thermal insulation properties that are similar to that of air. Moreover, the RP-hybridized graphene is prepared using a one-step ball milling process in 100% yield, and does not require solvent or produce waste. The preparation of the flame-retardant PI foams can be scaled as the starting materials are commercially available and the techniques employed are industrially compatible.

Tuning the Surface Properties of Graphene Oxide by Surface-Initiated Polymerization of Epoxides: An Efficient Method for Enhancing Gas Separation.

Here, we describe an in situ approach for growing polyepoxides from the surfaces of graphene oxide (GO) using a surface-initiated polymerization reaction. The polymerization methodology is facile and general as a broad range of epoxides carrying various functional groups have been successfully polymerized by simply adding GO powders in the epoxide monomers. The resultant polyepoxide grafted GO are found to show enhanced dispersibility in various common solvents and to exhibit increased d-spacing between the basal planes. In particular, grafting poly(2,3-epoxy-1-propanol) (PEP) to GO results in a composite (i.e., GO-g-PEP) that is dispersible in water and miscible with polyether block amide, i.e., Pebax MH 1657. Preliminary studies have indicated the membranes prepared using Pebax/GO-g-PEP composites exhibit enhanced CO2 permeabilities and selectivities in comparison to H2, O2, or N2. The excellent performance in gas separation is attributed to the layered structure of the GO-g-PEP sheets with enlarged d-spacing and the functional groups present on the PEP chains grafted to the surfaces of GO sheets.

Enhanced photoresponse of large-sized photoactive graphene composite films based on water-soluble conjugated polymers.

Composite films of chemically converted graphene (CCG) and water-soluble polythiophenes (P3TOPS and P3TOPA) were prepared by a LBL method using a suspension of negatively charged CCG-P3TOPS sheets and a solution of positively charged P3TOPA. The composite films show enhanced photoresponse due to photoinduced electron transfer from the polythiophenes to CCG.