Revealing Principles for Design of Lean-Electrolyte Lithium Metal Anode via In Situ Spectroscopy.

Lean-electrolyte conditions are highly pursued for practical lithium (Li) metal batteries. The previous studies on the Li metal anodes, in general, exhibited good stability with a large excess of electrolyte. However, the targeted design of Li hosts under relatively low electrolyte conditions has been rarely studied so far. Herein, we have shown that electrolyte consumption severely affects the cycling stability of Li metal anode. Considering carbon hosts as typical examples, we innovatively employed in situ synchrotron X-ray diffraction, in situ Raman spectroscopy, and theoretical computations to obtain a better understanding of the Li nucleation/deposition processes. We also showed the usefulness of in situ electrochemical impedance spectra to analyze interfacial fluctuation at the Li/electrolyte interface, together with nuclear magnetic resonance data to quantify electrolyte consumption. We have found that uneven Li nucleation/deposition and the crack of surface-area-derived solid-electrolyte interface (SEI) layer both lead to a great consumption of electrolyte. Then, we suggested a design principle for Li host to overcome the electrolyte loss, that is, uneven growth of the Li structure and the crack of the SEI layer must be simultaneously controlled. As a proof of concept, we demonstrated the usefulness of a 3D low-surface-area defective graphene host (L-DG) to control Li nucleation/deposition and stabilize the SEI layer, contributing to a highly reversible Li plating/stripping. As a result, such a Li host can achieve stable cycles (e.g., 1.0 mAh cm-2) with a low electrolyte loading (10 µL). This work demonstrates the necessity to design Li metal anodes under lean-electrolyte conditions and brings Li metal batteries a step closer to their practical applications.

ACQ-to-AIE Transformation: Tuning Molecular Packing by Regioisomerization for Two-Photon NIR Bioimaging.

The traditional design strategies for highly bright solid-state luminescent materials rely on weakening the intermolecular π-π interactions, which may limit diversity when developing new materials. Herein, we propose a strategy of tuning the molecular packing mode by regioisomerization to regulate the solid-state fluorescence. TBP-e-TPA with a molecular rotor in the end position of a planar core adopts a long-range cofacial packing mode, which in the solid state is almost non-emissive. By shifting molecular rotors to the bay position, the resultant TBP-b-TPA possesses a discrete cross packing mode, giving a quantum yield of 15.6±0.2 %. These results demonstrate the relationship between the solid-state fluorescence efficiency and the molecule's packing mode. Thanks to the good photophysical properties, TBP-b-TPA nanoparticles were used for two-photon deep brain imaging. This molecular design philosophy provides a new way of designing highly bright solid-state fluorophores.

Vortex fluidic regulated phospholipid equilibria involving liposomes down to sub-micelle size assemblies.

Conventional channel-based microfluidic platforms have gained prominence in controlling the bottom-up formation of phospholipid based nanostructures including liposomes. However, there are challenges in the production of liposomes from rapidly scalable processes. These have been overcome using a vortex fluidic device (VFD), which is a thin film microfluidic platform rather than channel-based, affording ∼110 nm diameter liposomes. The high yielding and high throughput continuous flow process has a 45° tilted rapidly rotating glass tube with an inner hydrophobic surface. Processing is also possible in the confined mode of operation which is effective for labelling pre-VFD-prepared liposomes with fluorophore tags for subsequent mechanistic studies on the fate of liposomes under shear stress in the VFD. In situ small-angle neutron scattering (SANS) established the co-existence of liposomes ∼110 nm with small rafts, micelles, distorted micelles, or sub-micelle size assemblies of phospholipid, for increasing rotation speeds. The equilibria between these smaller entities and ∼110 nm liposomes for a specific rotational speed of the tube is consistent with the spatial arrangement and dimensionality of topological fluid flow regimes in the VFD. The prevalence for the formation of ∼110 nm diameter liposomes establishes that this is typically the most stable structure from the bottom-up self-assembly of the phospholipid and is in accord with dimensions of exosomes.

Identification of microplastic fibres released from COVID-19 test swabs with Raman imaging.

Background: COVID-19 pandemic is not yet over, and it has been generating lots of plastic wastes that become a big concern. To catch the virus, for example, no matter via antigen or PCR test, swab is generally used for sampling. Unfortunately, the swab tip is commonly made of plastics, and thus it can be a potential source of microplastics. This study aims to propose and optimise several Raman imaging to identify the microplastic fibres released from different COVID-19 test swabs. Results: The results show that Raman imaging can effectively identify and visualise the microplastic fibres released from the swabs. In the meantime, on the surface of the fibres, additives such as titanium oxide particles are also captured for some brands of swabs. To increase the result certainty, scanning electron microscope (SEM) is first employed to get the morphology of the released microplastic fibres, along with Energy-dispersive X-ray spectroscopy (EDS) to confirm the presence of titanium element. Then, Raman imaging is advanced to identify and visualise the microplastics and titanium oxide particles, from different characteristic peaks in the scanning spectrum matrix. To further increase the imaging certainty, these images can be merged and cross-checked using algorithms, or the raw data from the scanning spectrum matrix can be analysed and decoded via chemometrics, such as principal component analysis (PCA). Beyond the advantages, the disadvantages of the confocal Raman imaging (affected by focal height) and algorithms (non-supervised calculation) are also discussed and intentionally corrected. In brief, the imaging analysis (particularly the combined SEM with Raman) is recommended to avoid the possible result bias that might be generated from the single spectrum analysis at a selective but random position. Conclusions: Overall, the results indicate that Raman imaging can be a useful tool to detect microplastics. The results also send us a strong warning that, if we worry about the potential microplastics contamination, we should be cautious to select the suitable COVID-19 testing kits. Supplementary Information: The online version contains supplementary material available at 10.1186/s12302-023-00737-0.

A simple strategy for the efficient design of mitochondria-targeting NIR-II phototheranostics.

The pursuit of phototheranostic agents with near-infrared II (NIR-II) emission, high photothermal conversion efficiency (PCE) and the robust generation of reactive oxygen species (ROS) in the aggregated state is always in high demand but remains a big challenge. Herein, we report a simple strategy to endow molecules with NIR-II imaging and photothermal therapy (PTT)/photodynamic therapy (PDT) abilities by equipping NIR-II aggregation-induced emission luminogens (AIEgens) with the cationic trimethylammonium unit, named as TDTN+. The resultant TDTN+ species can self-assemble into nanoparticles, which exhibit a maximum emission at ∼1052 nm, a high PCE (66.7%), type I and type II ROS generation and a mitochondria-targeting ability, simultaneously. The TDTN+ can realize brain imaging with bright fluorescence and an effective tumor killing effect. Overall, this work presents an innovative design strategy to develop multimodality phototheranostic agents.

Applying Raman imaging to capture and identify microplastics and nanoplastics in the garden.

The characterisation of microplastics is still a challenge, and the challenge is even greater for nanoplastics, of which we only have a limited knowledge so far. Herewith we employ Raman imaging to directly visualise microplastics and nanoplastics which are released from the trimmer lines during lawn mowing. The signal-noise ratio of Raman imaging is significantly increased by generating an image from hundreds or thousands of Raman spectra, rather than from a single spectrum, and is further increased by combining with the logic-based and PCA-based algorithms. The increased signal-noise ratio enables us to capture and identify microplastics and particularly nanoplastics, including plastic fragments or shreds (with diameters / widths of 80 nm - 3 µm) and nanoparticles (with diameters of < 1000 nm) that are released during the mimicked mowing process. Using Raman imaging, we estimate that thousands of microplastics (0.1-5 mm), and billions of nanoplastics (< 1000 nm), are released per minute when a line trimmer is used to mow lawn. Overall, Raman imaging provides effective characterisation of the microplastics and is particularly suitable for nanoplastics.

Raman imaging of microplastics and nanoplastics generated by cutting PVC pipe.

The characterisation of nanoplastics is much more difficult than that of microplastics. Herewith we employ Raman imaging to capture and visualise nanoplastics and microplastics, due to the increased signal-noise ratio from Raman spectrum matrix when compared with that from a single spectrum. The images mapping multiple characteristic peaks can be merged into one using logic-based algorithm, in order to cross-check these images and to further increase the signal-noise ratio. We demonstrate how to capture and identify microplastics, and then zoom down gradually to visualise nanoplastics, in order to avoid the shielding effect of the microplastics to shadow and obscure the nanoplastics. We also carefully compare the advantages and disadvantages of Raman imaging, while giving recommendations for improvement. We validate our approach to capture the microplastics and nanoplastics as particles released when we cut and assemble PVC pipes in our garden. We estimate that, during a cutting process of the PVC pipe, thousands of microplastics in the range of 0.1-5 mm can be released, along with millions of small microplastics in the range of 1-100 µm, and billions of nanoplastics in the range of <1 µm. Overall, Raman imaging can effectively capture microplastics and nanoplastics.

Raman imaging for the identification of Teflon microplastics and nanoplastics released from non-stick cookware.

The characterisation of microplastics is still difficult, and the challenge is even greater for nanoplastics. A possible source of these particles is the scratched surface of a non-stick cooking pot that is mainly coated with Teflon. Herein we employ Raman imaging to scan the surfaces of different non-stick pots and collect spectra as spectrum matrices, akin to a hyperspectral imaging process. We adjust and optimise different algorithms and create a new hybrid algorithm to extract the extremely weak signal of Teflon microplastics and particularly nanoplastics. We use multiple characteristic peaks of Teflon to create several images, and merge them to one, using a logic-based algorithm (i), in order to cross-check them and to increase the signal-noise ratio. To differentiate the varied peak heights towards image merging, an algebra-based algorithm (ii) is developed to process different images with weighting factors. To map the images via the whole set of the spectrum (not just from the individual characteristic peaks), a principal component analysis (PCA)-based algorithm (iii) is employed to orthogonally decode the spectrum matrix to the PCA spectrum and PCA intensity image. To effectively extract the Teflon spectrum information, a new hybrid algorithm is developed to justify the PCA spectra and merge the PCA intensity images with the algebra-based algorithm (PCA/algebra-based algorithm) (iv). Based on these developments and with the help of SEM, we estimate that thousands to millions of Teflon microplastics and nanoplastics might be released during a mimic cooking process. Overall, it is recommended that Raman imaging, along with the signal recognition algorithms, be combined with SEM to characterise and quantify microplastics and nanoplastics.

Fire releases micro- and nanoplastics: Raman imaging on burned disposable gloves.

Raman imaging can effectively characterise microplastics and nanoplastics, which is validated here to capture the items released from the plastic gloves when subjected to a mimicked fire. During the COVID-19 pandemic, large quantities of personal protective equipment (PPE) units have been used, such as the disposable gloves. If discarded and poorly managed, plastics gloves might break down to release secondary contaminants. The breakdown process can be accelerated by burning in a bushfire or at the incineration plants. During the burning process, the functional groups on the surface can be burned differently due to their different thermal stabilities. The different degrees of burning can be distinguished and visualised via Raman imaging. In the meantime, at the bottom of the burned plastics, microplastics and nanoplastics can be generated at a significant amount. The possible false Raman imaging on microplastics and nanoplastics is also discussed, by effectively extracting and distinguishing the weak signal from the background or noise. Overall, these findings confirm the importance of effectively working waste incineration plants and litter prevention, and suggest that Raman imaging is a suitable approach to characterise microplastics and nanoplastics.

Assessment of microplastics and nanoplastics released from a chopping board using Raman imaging in combination with three algorithms.

As contaminants of emerging concern, microplastics and nanoplastics are ubiquitous in not only aquatic and terrestrial environments but also household settings. While the characterisation of microplastics is still a challenge, the analysis of nanoplastics is even more difficult. In this study, we aim to examine several novel algorithmic methods intended for analysing complex Raman spectrum matrices towards visualisation of plastic particles released from a chopping board. Specifically, we compare and advance three decoding algorithms, including (i) a logic-based algorithm to merge and cross-check multiple Raman images that map the intensities of several characteristic peaks; (ii) a principal component analysis-based algorithm to generate intensity images from whole sets of spectra, not just from individual characteristic peaks; (iii) an algebra-based algorithm to merge and cross-check the loading matrix to enhance characterisation efficiency. Assisted with a scanning electron microscope, we estimate that 100-300 microplastics / nanoplastics per mm per cut along the groove formed on the chopping board, and ~3000 per mm2 per cut in the scratched area, may be released from a chopping board during food preparation and may be subsequently ingested by human. Overall, the Raman imaging combined with algorithms can provide effective characterisation of microplastics and nanoplastics.

Molecular Crystal Engineering of Organic Chromophores for NIR-II Fluorescence Quantification of Cerebrovascular Function.

Although molecular design strategies for highly bright near-infrared II (NIR-II) fluorophores were proposed, the lack of solid structural identification (single crystal) hinders the further development of this field. This thorny issue is addressed by performing the structure-function relationship of NIR-II dyes, as confirmed by molecular single crystal engineering. Single crystal structure analysis confirms that twisted architectures (large dihedral angles ∼70°) and loose packing patterns (intermolecular distance of ∼3.4-4.5 Å) are key elements to enhance the absolute quantum yield (QY) in the solid state. Through regulating donor-acceptor distance and donor-acceptor interactions, the resultant well-defined TBP-b-DFA fluorophore displays an absolute QY of 0.4% with an emission extending to 1400 nm, which is favorable for NIR-II bioimaging. The cerebrovascular function, including cerebral blood flow and cerebrovascular reactivity of different conditions, is accurately quantified by a NIR-II fluorescence wide-field microscope. Our study provides a sight for designing NIR-II fluorophores, which is useful for studying cerebrovascular function.

Vortex fluidic induced mass transfer across immiscible phases.

Mixing immiscible liquids typically requires the use of auxiliary substances including phase transfer catalysts, microgels, surfactants, complex polymers and nano-particles and/or micromixers. Centrifugally separated immiscible liquids of different densities in a 45° tilted rotating tube offer scope for avoiding their use. Micron to submicron size topological flow regimes in the thin films induce high inter-phase mass transfer depending on the nature of the two liquids. A hemispherical base tube creates a Coriolis force as a 'spinning top' (ST) topological fluid flow in the less dense liquid which penetrates the denser layer of liquid, delivering liquid from the upper layer through the lower layer to the surface of the tube with the thickness of the layers determined using neutron imaging. Similarly, double helical (DH) topological flow in the less dense liquid, arising from Faraday wave eddy currents twisted by Coriolis forces, impact through the less dense liquid onto the surface of the tube. The lateral dimensions of these topological flows have been determined using 'molecular drilling' impacting on a thin layer of polysulfone on the surface of the tube and self-assembly of nanoparticles at the interface of the two liquids. At high rotation speeds, DH flow also occurs in the denser layer, with a critical rotational speed reached resulting in rapid phase demixing of preformed emulsions of two immiscible liquids. ST flow is perturbed relative to double helical flow by changing the shape of the base of the tube while maintaining high mass transfer between phases as demonstrated by circumventing the need for phase transfer catalysts. The findings presented here have implications for overcoming mass transfer limitations at interfaces of liquids, and provide new methods for extractions and separation science, and avoiding the formation of emulsions.

Optical-Based Biosensors and Their Portable Healthcare Devices for Detecting and Monitoring Biomarkers in Body Fluids.

The detection and monitoring of biomarkers in body fluids has been used to improve human healthcare activities for decades. In recent years, researchers have focused their attention on applying the point-of-care (POC) strategies into biomarker detection. The evolution of mobile technologies has allowed researchers to develop numerous portable medical devices that aim to deliver comparable results to clinical measurements. Among these, optical-based detection methods have been considered as one of the common and efficient ways to detect and monitor the presence of biomarkers in bodily fluids, and emerging aggregation-induced emission luminogens (AIEgens) with their distinct features are merging with portable medical devices. In this review, the detection methodologies that use optical measurements in the POC systems for the detection and monitoring of biomarkers in bodily fluids are compared, including colorimetry, fluorescence and chemiluminescence measurements. The current portable technologies, with or without the use of smartphones in device development, that are combined with optical biosensors for the detection and monitoring of biomarkers in body fluids, are also investigated. The review also discusses novel AIEgens used in the portable systems for the detection and monitoring of biomarkers in body fluid. Finally, the potential of future developments and the use of optical detection-based portable devices in healthcare activities are explored.

Natural-based Hydrogels: A Journey from Simple to Smart Networks for Medical Examination.

Natural hydrogels, due to their unique biological properties, have been used extensively for various medical and clinical examinations that are performed to investigate the signs of disease. Recently, complex-crosslinking strategies improved the mechanical properties and advanced approaches have resulted in the introduction of naturally derived hydrogels that exhibit high biocompatibility, with shape memory and self-healing characteristics. Moreover, the creation of self-assembled natural hydrogels under physiological conditions has provided the opportunity to engineer fine-tuning properties. To highlight recent studies of natural-based hydrogels and their applications for medical investigation, a critical review was undertaken using published papers from the Science Direct database. This review presents different natural-based hydrogels (natural, natural-synthetic hybrid and complex-crosslinked hydrogels), their historical evolution, and recent studies of medical examination applications. The application of natural-based hydrogels in the design and fabrication of biosensors, catheters and medical electrodes, detection of cancer, targeted delivery of imaging compounds (bioimaging) and fabrication of fluorescent bioprobes is summarised here. Without doubt, in future, more useful and practical concepts will be derived to identify natural-based hydrogels for a wide range of clinical examination applications.

Novel Bacterial Cellulose-Poly (Acrylic Acid) Hybrid Hydrogels with Controllable Antimicrobial Ability as Dressings for Chronic Wounds.

This investigation examines the combination of poly (acrylic acid) (PAA) and bacterial cellulose (BC) nanofibers to synthesize hydrogel hybrid composites used for wound dressing application. Amoxicillin (AM) was also grafted onto the composites for drug release. Fourier transform infrared analysis and scanning electron microscopy conducted revealed the structure and porosity of the composite being developed, as well as the successful fabrication of BC-PAA composites. The results of mechanical testing and hygroscopicity revealed that the composite shows higher stability than hydrogels which are currently used worldwide, albeit with a slight reduction in swelling capabilities. However, the composite was revealed to be responsive to a rise in pH values with an increase in composite swelling and drug release. These results together with their morphological characteristics suggest that BC-PAA hydrogel hybrid composite is a promising candidate for wound dressing application.