Nile Red Research Articles

Construction of an Artificial Light-Harvesting System with Photocatalytic Activity Based on Nor-seco-cucurbit[10]uril in Aqueous Solution.

A supramolecular assembly was constructed based on the tetraphenylethylene derivatives (TPEs) and nor-seco-cucurbit[10]uril (ns-Q[10]). Upon introduction of the dye Rhodamine B (RB) into the TPEs@ns-Q[10] assembly, an energy transfer process can occur from the TPEs@ns-Q[10] assembly to RB. Moreover, after the addition of Nile Red (NiR), a two-step sequential energy transfer process from the TPEs@ns-Q[10] assembly to RB and then to NiR can occur. Additionally, the dye Eosin Y (ESY) was introduced into the TPEs@ns-Q[10] assembly and an energy transfer process can take place from the TPEs@ns-Q[10] assembly to ESY. To utilize the harvested energy from the TPEs@ns-Q[10]-RB-NiR and TPEs@ns-Q[10]-ESY system, we applied the TPEs@ns-Q[10] assembly-based light-harvesting systems (LHSs) as a catalyst for the advancement of the photocatalytic dehalogenation reaction in aqueous solution. When promoted with 0.5 mol % catalyst, the reaction yield reached 78 and 68%, demonstrating the promising potential of TPEs@ns-Q[10] assembly-based LHSs in the promotion of the photocatalytic dehalogenation reaction.

Surface Nanodroplet‐Confined Engineering of Gold (I) ‐Thiolate Nanostructures

AbstractGold(I)‐thiolate complexes have served as primary building blocks for diverse Au nanostructure synthesis strategies. A delicate approach to characterize and control Au(I)‐thiolate motif formation and assembly on the surface is needed as it can potentially solve challenges associated with utilizing gold nanomaterials in many applications. Here, the controllable generation of flower‐shaped surface gold nanostructures (FSGNs) is demonstrated by manipulating the formation‐assembly process of Au(I)‐dodecanethiolate motifs within nanoscale surface droplets. The morphology and structure of the resulting Au nanostructures are governed by internal convection flows and interfacial energy, modulated by the nanodroplet composition and substrate wettability. The obtained FSGNs are proven to act as versatile scaffolds for the selective generation of Au spiky nanostars. These FSGNs can also be utilized to functionalize nanodroplet‐based reactors, boosting the fluorescent intensity of Nile red (NR) fluorophores and decomposing NR via catalytic reaction. Remarkably, with FSGN functionalized droplets smaller than a radius of 500 nm, the decomposition rate of NR can reach ≈0.01 s−1. These results highlight a miniaturized, controllable, and automated method for the in situ production of 3D gold nanostructures on substrates, offering prospects for fast surface nanostructure fabrication and efficient environmental pollutant treatment.

The LiaSR Two-Component System Regulates Resistance to Chlorhexidine in Streptococcus mutans.

Chlorhexidine (CHX) is widely considered to be the gold standard for preventing dental caries. However, it is possible to induce resistance to CHX. The LiaSR two-component system has been identified that contributed to CHX resistance in Streptococcus mutans, which is one of the major pathogens in dental caries. However, the underlying mechanisms remain unclear. In this study, an MIC assay and a viability assessment demonstrated that after deleting the liaS and liaR genes, the sensitivity of mutants could increase. The Nile Red efflux assay exhibited that the efflux rates of mutants were significantly decreased. The RT-qPCR results indicated that the LiaSR two-component system-mediating influence on the expression of lmrB in S. mutans contributed to the efflux rate. The hydrophobicity assay and membrane potential assay showed that the mutants had higher levels of hydrophobicity and depolarization, suggesting that their membranes were more easily disturbed. The TEM graphs revealed that the border of the cell membrane was unclear in mutants compared with the wild-type strain, indicating that the cell envelope's stress response may have been inhibited. While the surface charge of mutants showed no significant difference in the wild-type strain according to the result of cytochrome c-based charged determination. This study provides valuable novel insights into the mechanisms of the LiaSR two-component system in the CHX resistance of S. mutans.

Analytical Methods for Extraction of Microplastics from Compost in Sri Lanka

Microplastics (MP) are the plastics with 1 μm-5 mm dimensions. Meanwhile, compost has been identified as a major source of MP in the soil, although compost is a great plant nutrient source, and it provides tremendous benefits for crops. This is primarily ascribed to most of the compost being produced through Municipal Solid Waste Management projects. However, due to the detrimental impacts on soil’s biological, physical, and chemical health, together with the high accumulation probability of MP caused by repeated application of compost, regulations should be implemented on the limitation of MP in compost. Even though there are a few different methods available in the literature for MP extraction and quantification in organic matter (OM)-rich matrices, like compost, sludge, and sediments, a properly validated, routine analytical procedure is missing in Sri Lanka Standards (SLS). Therefore, in this project, the effectiveness of four different MP extraction methods in the literature were compared and validated for compost, to implement an MP analysis method suitable for compost specifications in the SLS. The methodologies included MP extraction by density separation using NaCl or ZnCl2 solutions followed by digestion of OM using 30% KOH: NaOCl solution or Fenton’s reagent. The common MP analysis method for the four protocols was staining with the hydrophobic, fluorescent stain Nile Red, and visual observation. Digestion efficiency of OM and spike recovery of Polystyrene (PS), Polyvinyl Chloride (PVC), Polyethylene terephthalate (PET), High-Density Polyethylene (HDPE), and Polypropylene (PP) microplastics in 1-2 mm dimension by the four MP extraction methods were compared for the validation. T-tests (confidence level=95%) were carried out to determine the significant difference between the OM digestion efficiency in each of the four methods. Each of the combinations compared was significantly different from the other except for ZnCl2/Fenton and NaCl/30% KOH:NaOCl comparison. Meanwhile, the OM removal by ZnCl2/Fenton and NaCl/30% KOH:NaOCl excluding the density separation step also was not significantly different. The spike recovery analysis showed ZnCl2/Fenton combination as the best out of the tested combinations with above 95% recovery percentages for PS, PVC, PP and 100 for HDPE and PET by particle count. However, precipitate formations in the ZnCl2/Fenton combination might cause false negative or positive results for spike recovery when applied to the real samples with smaller MP. The extraction reagents, NaCl was not an ideal solution and ZnCl2 was a good solution for the MP types used. Moreover, in this project, double digestion of OM with NaCl/30% KOH:NaOCl before and after the density separation with ZnCl2 is suggested as a novel and more effective OM digestion protocol before Nile Red staining, and further validations are suggested prior to its final implementation.
 
 Keywords: Microplastics, Compost, Extraction, Organic matter

Spectral Investigations of Fluorescence Tracers in Automotive and Aviation Fuels under Cryogenic Conditions

This study investigated spectral laser-induced fluorescence signals of dyes in fuels for automotive and aerospace applications under low temperatures and cryogenic conditions down to 183 K. For this purpose, a fluorescence chamber was developed based on cooling with liquid nitrogen. The design enabled a minimal inner chamber temperature of 153 K. Furthermore, the applicability of two-color LIF for liquid thermometry was evaluated under these conditions. The temperature determination was based on the temperature-sensitive fluorescence intensity ratio of the special dyes doped into the fuels determined in suitable spectral regions, which represented common bandpass filters. For this purpose, the fluorescence signals of the dye doped into the gasoline and jet fuel surrogate isooctane were tested as well as blends of isooctane and the ethanol biofuels E20 (comprising 80 vol.% isooctane and 20 vol.% ethanol), E40, and E100. Additionally, a realistic multi-component fuel Jet A-1 mixed with a suitable fluorescence dye was investigated. E100 was doped with Eosin-Y, and the remaining fuels were doped with Nile red. Temperature-dependent spectral LIF intensities were recorded in the range of 183 K–293 K, which simulate extreme environments for aerospace and automotive applications. Frozen fuel–dye mixtures cause significant extinction effects and prevent sufficient signal detection at low and cryogenic temperatures, defining the detection limit. A temperature decrease led to a spectral shift in the emission peaks of E100 doped with Eosin-Y toward shorter wavelengths, while the spectra of mixtures doped with Nile red were shifted toward longer wavelengths. The suggested bandpass filters produced the temperature-sensitive intensity ratio (the average over the temperature interval) of the dyes with the largest sensitivity for Jet A-1 (5.2%/K), followed by E100 (4.95%/K), E40 (4.07%/K), E20 (3.23%/K), and isooctane (3.07%/K), even at cryogenic temperatures.

Tunable self-assembly of lipid-based block polymeric micelles with temperature-sensitive poly(vinylcaprolactam) shell for effective anticancer drug delivery

Lipids, as naturally occurring biomolecules have emerged as promising carriers for delivering various therapeutic agents. However, only a few attempts have been made in terms of their applications as amphiphilic block copolymers for anticancer drug delivery. In this work, a biocompatible micellar drug delivery system with fatty acid-based polymer core and temperature-sensitive shell was developed. A series of amphiphilic block copolymers poly(vinyl stearate)/poly(vinyl laurate)-b-poly(N-vinylcaprolactam) (PVS/PVL-b-PNVCL) were synthesized via microwave-assisted reversible addition-fragmentation chain transfer polymerization in a controlled fashion. By varying the fatty acid type and hydrophilic/hydrophobic block lengths, the self-assembly behaviour of the block copolymer micelles proved to be highly tunable in terms of their morphology and particle size. Nile Red and hydrophobic anticancer drug doxorubicin (DOX) were effectively incorporated into the micelles, demonstrating high drug loading capacity, good serum stability, and temperature-dependent drug release characteristics of the polymeric micelles. In vitro studies using cell models revealed that blank PVS -b-PNVCL micelles are biocompatible with different cell lines, while DOX-loaded micelles were internalized into and accumulated in the cells, showing a high cytotoxic effect against HeLa cells. These findings suggest an opportunity for the development of safe and efficient lipid-based micellar system for smart drug delivery and cancer treatments.

Self‐assembly and degradation of photolabile diblock bottlebrushes

AbstractAqueous self‐assembly of amphiphilic block copolymers form diverse nanostructured morphologies depending on block volume fraction and solvophilicity. Stimuli‐responsive motifs have been combined with self‐assembled micelles to afford spatiotemporal, on‐demand encapsulation and payload release. However, the role of modular polymer architecture (i.e., bottlebrushes) in stimuli‐responsive aqueous self‐assembly is not fully understood. The synthesis, aqueous self‐assembly, and photoirradiation of photolabile, amphiphilic bottlebrush block copolymers is presented herein. Specifically, the efficient photoscission of o‐nitrobenzene motifs at the junction of a poly(norbornene o‐nitrobenzene polystyrene)‐block‐poly(norbornene polyethylene glycol) diblock bottlebrush side chain and backbone cleaved away hydrophobic polystyrene side chains and artificially increased the volume fraction of poly(ethylene glycol) (fPEG). In doing so, self‐assembled micelles readily degrade to micelle‐to‐micelle and micelle‐to‐aggregate structures after photoirradiation. Finally, this bottlebrush micelle system is used to demonstrate the efficient encapsulation and stimuli‐responsive release of Nile Red that is monitored by fluorescence spectroscopy and dynamic light scattering. The contribution of this work expands the utility of amphiphilic bottlebrush systems as highly efficient and responsive, hierarchically assembled nanomaterials.

Optimized Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) Production by Moderately Haloalkaliphilic Bacterium Halomonas alkalicola Ext

Polyhydroxyalkanoates (PHAs) are biodegradable and biocompatible polymers that are produced by microorganisms as storage materials under limited nutrition and excess carbon. These PHAs have been found to be ideal for replacing synthetic plastics for use in packaging and biomedical applications. In this study, an alkaliphilic and moderately halophilic bacterium Halomonas alkalicola Ext was isolated from Lake Simbi Nyaima in western Kenya and investigated for PHA production. Sudan Black B and Nile Red A staining showed that bacterium had distinct ability for accumulation of PHAs. To optimize PHA production, the bacterium was grown in submerged fermentation under varying culture conditions and different sources and concentrations of carbon and nitrogen. With one-factor-at-a-time (OFTA) approach, optimal PHA yields were obtained after 72 hours at a pH of 10.0, temperature of 35°C, and 2.5% (w/v) NaCl. The bacterium yielded the highest biomass, and PHA amounts on 2% galactose and 0.1% ammonium sulfate as sources of carbon and nitrogen, respectively. A record PHA yield of 0.071 g g-1 with a titer of 1.419±0.09 g/L was achieved from 3.397 g/L of biomass, equivalent to 41.8% PHA content. Using response surface methodology, PHA titer was increased by 1.5% to 1.44 g/L, while PHA content was improved 1.1-fold to 45.57%. Polymer analysis revealed that the extracted PHA was a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) (3−HB:3−HV=92:8) with two copolymer subunits of 3-hydroxyvaryrate (3-HB) and 3-hydroxybutyrate (3-HV). Halomonas alkalicola Ext attained efficient galactose conversion into PHBV under high salinity and alkalinity conditions.

Construction and Performance Study of Artificial Light‐harvesting Based on Al3+ Fluorescence Regulation

AbstractA light‐emission system coordinating the amide 2‐amino‐3‐5‐dibromo‐N‐((2‐hydroxy‐naphthalene) benzoylhydrazine (R) and Al3+ was successfully prepared. Compared with that of R, the fluorescence emission band of the R–Al3+ group considerably improved. Therefore, using the R–Al3+ complex as a donor and two dyes (Nile Red and SR101) as acceptors, two artificial light–harvesting systems (ALHSs) were prepared. The energy transfer processes of the R–Al3+–Nile Red and R–Al3+–SR101 systems were confirmed. The findings will help in improving the current situation of ALHSs and have potential application value in ion detection and energy development.

Agricultural fertilisers contribute substantially to microplastic concentrations in UK soils

Since their invention, plastics have driven a revolution in behavior in all aspects of our lives, including agriculture. In-use and as a waste material, plastics degrade and accumulate in agricultural systems. Accumulation of plastic pollution in agricultural systems has negative impacts on human health and agricultural productivity but little is known about concentrations of microplastics in soils. Here we used a historical time series to examine changes to microplastic concentrations in agricultural soils over time. Microplastics were stained with Nile Red and quantified using fluorescence microscopy. We demonstrate that microplastic concentrations increased at higher rates in soils that are amended with either organic or inorganic fertiliser between 1966 and 2022, suggesting that agricultural fertilisers are an important contributor to microplastic concentrations in agricultural soils over time. This study provides evidence that agricultural soils are receptors and reservoirs of microplastic pollution, a legacy which is growing over time.

Optically monitoring the microenvironment of a hydrophobic cargo in amphiphilic nanogels: influence of network composition on loading and release.

Amphiphilic nanogels (ANGs) are promising carriers for hydrophobic cargos such as drugs, dyes, and catalysts. Loading content and release kinetics of these compounds are controlled by type and number of hydrophobic groups in the amphiphilic copolymer network. Thus, understanding the interactions between cargo and colloidal carrier is mandatory for a tailor-made and cargo-specific ANG design. To systematically explore the influence of the network composition on these interactions, we prepared a set of ANGs of different amphiphilicity and loaded these ANGs with varying concentrations of the solvatochromic dye Nile Red (NR). Here, NR acts as a hydrophobic model cargo to optically probe the polarity of its microenvironment. Analysis of the NR emission spectra as well as measurements of the fluorescence quantum yields and decay kinetics revealed a decrease in the polarity of the NR microenvironment with increasing hydrophobicity of the hydrophobic groups in the ANG network and dye-dye interactions at higher loading concentrations. At low NR concentrations, the hydrophobic cargo NR is encapsulated in the hydrophobic domains. Increasing NR concentrations resulted in probe molecules located in a more hydrophilic environment, i.e., at the nanodomain border, and favored dye-dye interactions and NR aggregation. These results correlate well with release experiments, indicating first NR release from more hydrophilic network locations. Overall, our findings demonstrate the importance to understand carrier-drug interactions for efficient loading and controlled release profiles in amphiphilic nanogels.

Probing the heterogeneity of molecular level organization of ionic liquids: a comparative study using neutral Nile red and cationic Nile blue sulfate as fluorescent probes for butyrolactam-based protic ionic liquids.

Ionic liquids (ILs) are liquid salts composed of cations and anions, known for their significant local heterogeneity at the molecular level. To understand the microheterogeneity with regard to their local polarity and local viscosity, we have used two structurally similar but chemically distinguishable fluorescent probes: Nile red (NR), a neutral molecule, and Nile blue sulfate (NBS), a charged molecule. A comparative study of the response of the two probes to the molecular level heterogeneity of ILs is expected to provide a better clarity of understanding regarding the charged polar domain and the uncharged hydrophobic domain of ILs. Towards this, we synthesized two butyrolactam-based protic ionic liquids (PILs), i.e., BTF and BTD, with the same ionic headgroup ([BT]+) and different alkyl tails ([RCOO]-), where {R = H, C11H23}. BTF has no significant hydrophobic domain, whereas BTD has a larger hydrophobic domain. Temperature-dependent fluorescence parameters such as fluorescence intensity, lifetime, and anisotropy were measured for both NR and NBS molecules. The use of a pair of structurally similar but ionically different probes enables differential estimation of parameters like the microviscosity of a domain using the fluorescence anisotropy parameter (r). The absorption and emission spectra of both probe molecules are observed to be blue shifted upon going from BTF to BTD. NR showed a significant blue shift in absorption and emission band maxima. Conversely, NBS exhibited a small wavelength shift, possibly influenced by the preferred location of their charged head group domain. Temperature-dependent rotational relaxation time (θ) of NR in BTD is smaller than that of NBS by 60-70%, indicating that stronger charge-charge interactions exist between the polar domain of BTD and NBS. Moreover, it is observed that the local viscosity of the BTF IL around both probes is similar, whereas there is a considerable difference for the BTD IL. These results are an indication that NBS being charged prefers to locate itself in the charged head group region of the IL, whereas NR being neutral tends to reside both in the hydrophobic domain and in the head group but is predominantly located in the hydrophobic domain.

A Nile red dye cathode with an asymmetric redox unit for lithium organic batteries.

A Nile red (NR) dye cathode with an asymmetric redox structure of para CN and CO bonds was developed for use in an efficient lithium organic battery with a good capacity of 125 mA h g-1 and two visible discharge/charge voltage plateaus (≈2.0 V and ≈1.7 V). The NR cathode demonstrated the advantages of employing cost-effective dyes to achieve multigradient voltage platform regulation.

Enhancing drug delivery with supramolecular amphiphilic macrocycle nanoparticles: selective targeting of CDK4/6 inhibitor palbociclib to melanoma.

Drug delivery systems based on amphiphilic supramolecular macrocycles have garnered increased attention over the past two decades due to their ability to successfully formulate nanoparticles. Macrocyclic (MC) materials can self-assemble at lower concentrations without the need for surfactants and polymers, but surfactants are required to form and stabilize nanoparticles at higher concentrations. Using MCs to deliver both hydrophilic and hydrophobic guest molecules is advantageous. We developed two novel types of amphiphilic macrocycle nanoparticles (MC NPs) capable of delivering either Nile Red (NR) (a hydrophobic model) or Rhodamine B (RhB) (a hydrophilic model) fluorescent dyes. We extensively characterized the materials using various techniques to determine size, morphology, stability, hemolysis, fluorescence, loading efficiency (LE), and loading capacity (LC). We then loaded the CDK4/6 inhibitor Palbociclib (Palb) into both MC NPs using a solvent diffusion method. This yielded Palb-MC NPs in the size range of 65-90 nm. They exhibited high stability over time and in fetal bovine serum with negligible toxicity against erythrocytes. Cytotoxicity was minimal when tested against RAW macrophages, human fibroblast HDFn, and adipose stromal cells (ASCs) at higher concentrations of MC NPs. Cell viability studies were conducted with different concentrations of MC NPs, Palb-MC NPs, and free Palb against RAW macrophages, human U-87 GBM, and human M14 melanoma cell lines in vitro. Flow cytometry experiments revealed that blank MC NPs and Palb-MC NPs were selectively targeted to melanoma cells, resulting in cell death compared to the other two cell lines. Future work will focus on studying the biological effect of MC NPs including their binding affinity with molecules/receptors expressed on the M14 and other melanoma cell surfaces by molecular docking simulations. Subsequently, we will evaluate the MCs as a component of combination therapy in a murine melanoma model.

Antibacterial activity of hydrophobicity modulated cationic polymers with enzyme and pH-responsiveness.

The membrane lipid compositions of prokaryotic and eukaryotic cells are inherently different in many aspects, although some similarities exist in their structure and composition. Therefore, selective targeting of membrane lipids with a compound of therapeutic value, such as an antibacterial copolymer, is often challenging. Hence, developing an ideal copolymer with antibacterial properties demands hydrophobicity/hydrophilicity balance with a high biosafety profile. To integrate hydrophobic/hydrophilic balance and cationic charge in an alternating antibacterial copolymer with enzyme and pH-responsiveness, a lysine appended styrenic monomer was copolymerized with a fatty acid (octanoic acid (OA) or myristic acid (MA)) tethered maleimide monomer via reversible addition-fragmentation chain transfer (RAFT) polymerization. A range of microscopic analyses, including dynamic light scattering (DLS), confirmed the formation of nanoaggregates (size ∼30-40 nm) by these polymers in aqueous solution with positive zeta potential (cationic surface charge). Hydrophobic Nile red (NR) dye was successfully encapsulated in the nanoaggregates, and the in vitro release kinetics of the NR dye were monitored at different pHs and in the presence or absence of esterase/lipase. The in vitro release kinetics of NR revealed ∼85% dye release in the presence of pH 5.5 and lipase, suggesting their suitability for pH/enzyme-triggered therapeutic payload delivery. The standard broth microdilution assay showed significant bactericidal activity against both Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria with an MIC50 value <30 μg mL-1. The effect of polymeric nanoaggregates on bacterial morphology and in vitro survival was further confirmed by field emission scanning electron microscopy (FESEM), agar gel disk diffusion assay, and bacterial live/dead cell count. The significantly low hemolytic activity against red blood cells (RBCs) (HC50 >103 μg mL-1) and nontoxic effect on human intestinal epithelial cells (INT 407) (EC50 >500 μg mL-1) ensure that the polymer nanoaggregates are safe for in vivo use and can serve as a potent antibacterial polymer.

Homeopathic potencies can regulate the growth and toxicity of Raphidiopsis raciborskii (cyanobacteria) and are traceably by solvatochromic dyes

Introduction: Cyanobacteria are found worldwide and can produce cyanotoxins. Since homeopathic potencies can modulate toxicity in different biological models, this study proposes to investigate whether cyanobacteria toxins might also be the case. Objectives: a) to investigate if homeopathic potencies can improve the resilience of Artemia franciscana (brine shrimp) embryos to saxitoxin (cyanotoxin) and to control the growth of Raphidiopsis raciborskii in vitro; b) to verify if physicochemical parameters can be used to track homeopathic potencies in seawater or cyanobacteria medium, with special focus on the interaction with solvatochromic dyes. Method: Artemia franciscana cysts were cultivated in seawater in 96-well plates to evaluate the hatching rate, vitality, and gene expression of heat shock proteins (Hsp), after being challenged with R. raciborskii extract containing 2.5 µg/liter of saxitoxin and treated with different homeopathic potencies chosen from a screening process. Cultures of R. raciborskii maintained in ASM-1 medium were equally treated with previously screened homeopathic potencies, and their growth was monitored as a function of time. The physicochemical properties of treated water were evaluated by interacting with solvatochromic dyes and measuring pH, conductivity, and temperature. Results: A lower rate of hatching of Artemia franciscana cysts was observed after treatment with Nitric acidum 6cH (p=0.03), and a complete toxicity reversal with increased Hsp 26 and p26 gene expression was seen after treatment with Isotherapic (R. raciborskii extract) 200cH (p≤0.02). Nitric acidum 200cH and Mercurius solubilis 30cH limited the exponential growth of cyanobacteria (p≤0.003) regardless of their concentration. Coumarin 7 was a marker for Nitric acidum 6cH and Isotherapic (R. raciborskii extract) 200cH, even when inserted into seawater. Nile red was a marker for Nitric acidum 200cH and Mercurius solubilis 30cH, even when inserted into ASM-1 medium (p≤0.05). An increase in pH and endo/exothermal effects of the ASM-1 medium was observed after these treatments (p≤0.007). The physicochemical analyzes were optimized after the previous submission of the samples to a constant unidirectional 2400 Gauss magnetic flow. Conclusion: The Isotherapic 200cH improved Artemia franciscana bioresilience to saxitoxin itself; Nitric acidum 200cH and Mercurius solubilis 30cH limited the growth of R. raciborskii. In all cases, those homeopathic potencies that showed biological effects were traceable in the aqueous medium using solvatochromic dyes, especially when the samples were subjected to the magnetic field.

Micellular fluorescence resonance energy transfer based fluorescent ratiometric response to hydrocarbon analytes.

Fluorescence resonance energy transfer (FRET) has been utilised to develop numerous selective and sensitive fluorescent ratiometric sensors. Typically, FRET-based fluorescent ratiometric sensors rely on chemical interactions between the sensor and analyte to illicit a response, thus unreactive hydrocarbons are a neglected analyte and a source for new sensors. By containing an unbound donor-acceptor system within micelles, energy transfer is enabled by spatial confinement. This offers the potential of a ratiometric response as a hydrocarbon analyte is added. Introducing a hydrocarbon analyte to this system causes micelles to swell, increasing the donor-acceptor distance and thus reducing the amount of observed energy transfer. We present InP/ZnS quantum dot donors interacting with a Nile Red acceptor, confined by cetyltrimethylammonium bromide (CTAB)-based micelles. We alleviated spatial confinement of the pair within micelles using common laboratory solvents to represent hydrocarbons, (toluene, hexane and octadecene). We constructed calibration curves for each solvent and found effective sensing ranges of 0.009-0.21, 0.008-0.27 and 0.003-0.06 M for toluene, hexane and octadecene, respectively. This study contributes towards the development of new hydrocarbon sensors utilising this new mechanism.

Sensitized Emission Imaging Allows Nanoscale Surface Polarity Mapping of α-Synuclein Amyloid Fibrils.

When misfolded, α-Synuclein (α-Syn), a natively disordered protein, aggregates to form amyloid fibrils responsible for the neurodegeneration observed in Parkinson's disease. Structural studies revealed distinct molecular packing of α-Syn in different fibril polymorphs and variations of interprotofilament connections in the fibrillar architecture. Fibril polymorphs have been hypothesized to exhibit diverse surface polarities depending on the folding state of the protein during aggregation; however, the spatial variation of surface polarity in amyloid fibrils remains unexplored. To map the local polarity (or hydrophobicity) along α-Syn fibrils, we visualized the spectral characteristics of two dyes with distinct polarities-hydrophilic Thioflavin T (ThT) and hydrophobic Nile red (NR)─when both are bound to α-Syn fibrils. Dual-channel fluorescence imaging reveals uneven partitioning of ThT and NR along individual fibrils, implying that relatively more polar/hydrophobic patches are spread over a few hundred nanometers. Remarkably, spectrally resolved sensitized emission imaging of α-Syn fibrils provides unambiguous evidence of energy transfer from ThT to NR, implying that dyes of dissimilar polarity are in close proximity. Furthermore, spatially resolved fluorescence spectroscopy of the solvatochromic probe NR allowed us to quantitatively map the range and variation of the polarity parameter ET30 along individual fibrils. Our results suggest the existence of interlaced polar and nonpolar nanoscale domains throughout the fibrils; however, the relative populations of these patches vary considerably over larger length scales likely due to heterogeneous packing of α-Syn during fibrilization and dissimilar exposed polarities of polymorphic segments. The employed method may provide a foundation for imaging modalities of other similar structurally unresolved systems with diverse hydrophobic-hydrophilic topology.

Layered Double Hydroxides as an Intercalation System for Hydrophobic Molecules.

Layered double hydroxides (LDHs) have been extensively studied as drug delivery systems due to their favorable characteristics, including biocompatibility, high loading efficiency, and pH-responsive release. However, the current research predominantly focuses on LDHs as carriers for various anionic drugs, while there are only limited reports on LDHs as carriers for hydrophobic drugs. In this study, we successfully achieved the loading of a hydrophobic drug mimic, Nile red (NR), into LDHs using sodium dodecyl sulfate (SDS) as an intermediate storage medium. Furthermore, we optimized the experimental methods and varied the SDS/NR molar ratio to optimize this intercalation system. With an increase in the SDS/NR molar ratio from 2/1 to 32/1, the loading efficiency of LDH-SDS-NR for NR initially increased from 1.32% for LDH-SDS-NR_2/1 to 4.46% for LDH-SDS-NR_8/1. Then, the loading efficiency slightly decreased to 3.64% for LDH-SDS-NR_16.8/1, but then increased again to 6.31% for LDH-SDS-NR_32/1. We believe that the established method and the obtained results in this study broaden the application scope of LDHs as delivery systems for hydrophobic drugs and contribute to the further expansion of the application scope of LDHs.

A low-cost TICT-based staining agent for identification of microplastics: Theoretical studies and simple, cost-effective smartphone-based fluorescence microscope application

A novel staining agent, (5-(4-(diethylamino)benzylidene)− 1,3-dimethylpyrimidine-2,4,6(1 H,3 H,5 H)-trione) (DDB) was developed for the effective detection of environmentally harmful microplastics. DDB has competitive cost advantages, namely its facile synthesis and high yield, over Nile Red (NR), which is commonly used for microplastic staining. The unique photophysical properties of DDB, including emissive twisted intramolecular charge transfer (TICT) and aggregation-induced emission (AIE), were corroborated via spectroscopic investigations and density functional theory (DFT) calculations. Notably, DDB demonstrated superior selectivity for staining microplastics (polyethylene (PE), polyurethane (PU), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), and polyethylene terephthalate (PET)) over non-plastic materials in water. Furthermore, modulation of the solvent environment during the staining process yielded distinct fluorescence in both the green and red channels for specific types of plastic with the interplay between locally excited (LE) and TICT states. Treatment with 5% ethanol results in the selective staining of PE and PET with the emission of red fluorescence, whereas treatment with 30% ethanol facilitates the selective staining of PU, PVC, and PET with the emission of green fluorescence. Additionally, DDB could selectively stain microplastics in spiked soil and river water samples. Furthermore, a smartphone-based fluorescence microscope was developed at a cost below $100, validating the effective detection of microplastics stained with the newly synthesized DDB. The outcomes of this research demonstrate the potential of DDB as an economical and efficient agent for selective microplastic detection.