Ratiometric Fluorescent pH Sensing with Carbon Dots: Fluorescence Mapping across pH Levels for Potential Underwater Applications.

Ocean acidification has become a major climate change concern requiring continuous observation. Additionally, in the industry, pH surveillance is of great importance. Consequently, there is a pressing demand to develop robust and inexpensive pH sensors. Ratiometric fluorescence pH sensing stands out as a promising concept. The application of carbon dots in fluorescent sensing presents a compelling avenue for the advancement of pH-sensing solutions. This potential is underpinned by the affordability of carbon dots, their straightforward manufacturing process, low toxicity, and minimal susceptibility to photobleaching. Thus, investigating novel carbon dots is essential to identify optimal pH-sensitive candidates. In this study, five carbon dots were synthesized through a simple solvothermal treatment, and their fluorescence was examined as a function of pH within the range of 5-9, across an excitation range of 200-550 nm and an emission range of 250-750 nm. The resulting optical features showed that all five carbon dots exhibited pH sensitivity in both the UV and visible regions. One type of carbon dot, synthesized from m-phenylenediamine, displayed ratiometric properties at four excitation wavelengths, with the best results observed when excited in the visible spectrum at 475 nm. Indeed, these carbon dots exhibited good linearity over pH values of 6-9 in aqueous Carmody buffer solution by calculating the ratio of the green emission band at 525 nm to the orange one at 630 nm (I525nm/I630nm), demonstrating highly suitable properties for ratiometric sensing.

Fluorescence intensity and fluorescence lifetime measurements of various carbon dots as a function of pH.

Measurement and monitoring of pH are essential in both the industry and academia. It is therefore important to continue developing novel, low-cost pH sensors that provide increased accuracy over long periods of time. Particularly promising are sensors based on materials that show pH-dependent fluorescence intensity (FI) and lifetime (FL). Carbon dots (CDs) are emerging as promising candidates because of their low cost, ease of manufacturing, low toxicity, and negligible photobleaching. However, little has been done to quantify the FI and FL values of CDs. Here we report the characterisation of the pH-dependent FI and FL of four novel solvothermal synthesised CDs. The fifth CD is used as a reference sample and was synthesised following a published synthesis. The precursors for the CDs include disperse blue 1 dye, phloroglucinol, m-phenylenediamine (m-PD), N, and N-dimethylformamide (DMF). The average diameter size of the CDs ranges from 1.5 to 15 nm. An excitation wavelength of 452 nm with a bandwidth of 45 nm was used to quantify the fluorescence in the pH range 5-9. Three CDs show a decreasing trend in FI with pH, while two CDs show an increasing trend. None of the CDs shows strong FL dependence. The FL changes around 0.5 ± 0.2 ns across the tested pH range. We suggest that the differences in the fluorescence trends can be attributed to the precursors chosen for synthesising the CDs.

Carbon Dot Therapeutic Platforms: Administration, Distribution, Metabolism, Excretion, Toxicity, and Therapeutic Potential.

Ultrasmall nanoparticles are often grouped under the broad umbrella term of "nanoparticles" when reported in the literature. However, for biomedical applications, their small sizes give them intimate interactions with biological species and endow them with unique functional physiochemical properties. Carbon quantum dots (CQDs) are an emerging class of ultrasmall nanoparticles which have demonstrated considerable biocompatibility and have been employed as potent theragnostic platforms. These particles find application for increasing drug solubility and targeting, along with facilitating the passage of drugs across impermeable membranes (i.e., blood brain barrier). Further functionality can be triggered by various environmental conditions or external stimuli (i.e., pH, temperature, near Infrared (NIR) light, ultrasound), and their intrinsic fluorescence is valuable for diagnostic applications. The focus of this review is to shed light on the therapeutic potential of CQDs and identify how they travel through the body, reach their site of action, administer therapeutic effect, and are excreted. Investigation into their toxicity and compatibility with larger nanoparticle carriers is also examined. The future of CQDs for theragnostic applications is promising due to their multifunctional attributes and documented biocompatibility. As nanomaterial platforms become more commonplace in clinical treatments, the commercialization of CQD therapeutics is anticipated.

Fluorescent Magnesium Hydroxide Nanosheet Bandages with Tailored Properties for Biocompatible Antimicrobial Wound Dressings and pH Monitoring.

Magnesium hydroxide (Mg(OH)2) is hailed as a cheap and biocompatible material with antimicrobial potential; however, research aimed at instilling additional properties and functionality to this material is scarce. In this work, we synthesized novel, fluorescent magnesium hydroxide nanosheets (Mg(OH)2-NS) with a morphology that closely resembles that of graphene oxide. These multifunctional nanosheets were employed as a potent antimicrobial agent against several medically relevant bacterial and fungal species, particularly on solid surfaces. Their strong fluorescence signature correlates to their hydroxide makeup and can therefore be used to assess their degradation and functional antimicrobial capacity. Furthermore, their pH-responsive change in fluorescence can potentially act as a pH probe for wound acidification, which is characteristic of healthy wound healing. These fluorescent antimicrobial nanosheets were stably integrated into biocompatible electrospun fibers and agarose gels to add functionality to the material. This reinforces the suitability of the material to be used as antimicrobial bandages and gels. The biocompatibility of the Mg(OH)2-NS for topical medical applications was supported by its noncytotoxic action on human keratinocyte (HaCaT) cells.

Bioimaging of C2C12 Muscle Myoblasts Using Fluorescent Carbon Quantum Dots Synthesized from Bread.

Biocompatible carbon quantum dots (CQDs) have recently attracted increased interest in biomedical imaging owing to their advantageous photoluminescence properties. Numerous precursors of fluorescent CQDs and various fabrication procedures are also reported in the literature. However; the use of concentrated mineral acids and other corrosive chemicals during the fabrication process curtails their biocompatibility and severely limits the utilization of the products in cell bio-imaging. In this study; a facile; fast; and cost-effective synthetic route is employed to fabricate CQDs from a natural organic resource; namely bread; where the use of any toxic chemicals is eliminated. Thus; the novel chemical-free technique facilitated the production of luminescent CQDs that were endowed with low cytotoxicity and; therefore; suitable candidates for bioimaging sensors. The above mentioned amorphous CQDs also exhibited fluorescence over 360-420 nm excitation wavelengths; and with a broad emission range of 360-600 nm. We have also shown that the CQDs were well internalized by muscle myoblasts (C2C12) and differentiated myotubes; the cell lines which have not been reported before.

Quantum dot (QD)-based probes for multiplexed determination of heavy metal ions.

Heavy metal contamination is a major global concern and additive toxicity resulting from the exposure to multiple heavy metal ions is more pronounced than that induced by a single metal species. Quantum dots (QDs) have demonstrated unique properties as sensing materials for heavy metal ions over the past two decades. With the rapid development and deep understanding on determination of single heavy metal ion using QD probes, this technology has been employed for sensing multiple metal ions. This review (with 97 refs.) summarizes the progress made in recent years in methods for multiplexed determination of heavy metal ions using QDs. Following an introduction into the importance of simultaneous quantitation of multiple heavy metal ions in environmentally relevant settings, the review discusses the applications of different types of QDs, i.e. chalcogenide, carbon, polymer and graphene in this field. Determination strategies based on fluorometric, colorimetric and electrochemical responses were reviewed including the testing mechanisms and differentiation between various metal ions. In addition, current state of the art sensor constructions, i.e. immobilization of QDs on solid substrate and sensor arrays have been highlighted. A concluding section describes the limitations, opportunities and future challenges of the QD probes. We also compiled a comprehensive table of currently available literature. The listed papers provided information in the following categories, i.e. type of QDs used, ligands or other components in the probe, metal ions tested, medium/substrate of the probe, transduction methods, discrimination mechanism, limit of detection (LOD) and concentration range. Graphic abstract.

Incorporation of quantum carbon dots into a PVP/ZnO hydrogel for use as an effective hexavalent chromium sensing platform.

Hydrogels offer a unique medium for sensing applications as they can draw upon the benefits of both solid and liquid sensing platforms. Incorporation of functionalised fluorescent nanoparticles within the hydrogel matrix results in a three-dimensional nanocomposite capable of interacting with water-soluble analytes, facilitating quantitative sensing applications. Here, we report the solvothermal synthesis of a novel Polyvinylpyrrolidone assembled hydrogel stabilised with zinc oxide quantum dots which does not require additional organic crosslinkers. Functionalization of these hydrogel with novel, brightly photoluminescent 2-amino-2-methyl-1-propanol quantum carbon dots (quantum yield of 62.5%) results in a composite capable of specific interaction with hexavalent chromium. Quantitative fluorescence quenching measurements of the hydrogel composite in the presence of hexavalent chromium shows a limit of detection of 1.2 µM Cr6+ which is below maximum allowable concentrations for drinking water. The hydrogel composite is cheap to manufacture and can be injected into 96 well plates for high throughput analysis of environmental water samples. These results are encouraging for the development of hydrogels and polymetric films to be used as novel fluorescent sensing platforms for environmental diagnostic applications.

Foaming at the mouth: Ingestion of floral foam microplastics by aquatic animals.

Phenol-formaldehyde plastics are used globally as floral foam and generate microplastics that can enter the environment. This study is the first to describe how aquatic animals interact with this type of microplastic, and the resultant physiological responses. We analysed "regular foam" microplastics generated from petroleum-derived phenol-formaldehyde plastic, and "biofoam" microplastics generated from plant-derived phenol-formaldehyde plastic. Regular foam and biofoam microplastics showed similar FTIR spectra. Both types of microplastics were consumed by all six invertebrate species tested: the freshwater gastropod Physa acuta, the marine gastropod Bembicium nanum, the marine bivalve Mytilus galloprovincialis, adults and neonates of the freshwater crustacean Daphnia magna, the marine amphipod Allorchestes compressa, and nauplii of the marine crustacean Artemia sp. For all species, the occurrence of ingestion was similar for regular foam and biofoam microplastics. Biofoam microplastics leached more than twice as much phenolic compounds than regular foam microplastics. The leachates from regular foam and biofoam microplastics showed the same acute toxicity to Artemia nauplii (24-h LC50 = 27.4 mg mL-1 and 22.8 mg mL-1, respectively) and D. magna (48-h LC50 = 17.8 mg mL-1 and 15.3 mg mL-1, respectively). However, biofoam microplastic leachate was twice as toxic to embryos of the zebrafish, Danio rerio, compared with leachate from regular foam microplastic (96-h LC50 = 43.8 mg mL-1 vs 27.1 mg mL-1). Using M. galloprovincialis, we show that regular foam microplastic leachate and the physical presence of the microplastics exerted separate and cumulative effects on catalase (CAT) activity, glutathione-s-transferase (GST) activity and lipid peroxidation. Microplastic ingestion did not affect the activity of acetylcholinesterase (AChE). Taken together, these results show that phenol-formaldehyde microplastics can interact with a range of aquatic animals, and affect sublethal endpoints by leaching toxic compounds, and through the physical presence of the microplastics themselves.

Interfacial separation of concentrated dye mixtures from solution with environmentally compatible nitrogenous-silane nanoparticles modified with Helianthus annuus husk extract.

The capacity of an adsorbent to bind and remove dye from solution greatly depends on the type of functionalization present on the nanoparticles surface, and its interaction with the dye molecules. Within this study, nitrogenous silane nanoparticles were hydrothermally synthesized resulting in the formation of rapid and highly efficient adsorbents for concentrated mixed dyes. The amorphous silane nanoparticles exhibited a monolayer based mechanism of mixed dye adsorption with removal capacities between 416.67 and 714.29 mg/g of adsorbent. Dye removal was predominantly due to the electrostatic attraction between the positively charged silane nanoparticles (13.22-8.20 mV) and the negatively charged dye molecules (-54.23 mV). Addition of H. annuus extract during synthesis resulted in three times the surface area and 10 times increased pore volume compared to the positive control. XPS analysis showed that silane treatments had various nitrogen containing functionalities at their surface responsible for binding dye. The weak colloidal stability of silane particles (13.22-8.20 mV) was disrupted following dye binding, resulting in their rapid coagulation and flocculation which facilitated the separation of bound dye molecules from solution. The suitability for environmental applications using these treatments was supported by a bacterial viability assay showing >90% cell viability in treated dye supernatants.

Petroleum Hydrocarbon Contamination in Terrestrial Ecosystems-Fate and Microbial Responses.

Petroleum hydrocarbons represent the most frequent environmental contaminant. The introduction of petroleum hydrocarbons into a pristine environment immediately changes the nature of that environment, resulting in reduced ecosystem functionality. Natural attenuation represents the single, most important biological process which removes petroleum hydrocarbons from the environment. It is a process where microorganisms present at the site degrade the organic contaminants without the input of external bioremediation enhancers (i.e., electron donors, electron acceptors, other microorganisms or nutrients). So successful is this natural attenuation process that in environmental biotechnology, bioremediation has developed steadily over the past 50 years based on this natural biodegradation process. Bioremediation is recognized as the most environmentally friendly remediation approach for the removal of petroleum hydrocarbons from an environment as it does not require intensive chemical, mechanical, and costly interventions. However, it is under-utilized as a commercial remediation strategy due to incomplete hydrocarbon catabolism and lengthy remediation times when compared with rival technologies. This review aims to describe the fate of petroleum hydrocarbons in the environment and discuss their interactions with abiotic and biotic components of the environment under both aerobic and anaerobic conditions. Furthermore, the mechanisms for dealing with petroleum hydrocarbon contamination in the environment will be examined. When petroleum hydrocarbons contaminate land, they start to interact with its surrounding, including physical (dispersion), physiochemical (evaporation, dissolution, sorption), chemical (photo-oxidation, auto-oxidation), and biological (plant and microbial catabolism of hydrocarbons) interactions. As microorganism (including bacteria and fungi) play an important role in the degradation of petroleum hydrocarbons, investigations into the microbial communities within contaminated soils is essential for any bioremediation project. This review highlights the fate of petroleum hydrocarbons in tertial environments, as well as the contributions of different microbial consortia for optimum petroleum hydrocarbon bioremediation potential. The impact of high-throughput metagenomic sequencing in determining the underlying degradation mechanisms is also discussed. This knowledge will aid the development of more efficient, cost-effective commercial bioremediation technologies.

Detection of helminth ova genera using in-situ biosynthesis of gold nanoparticles.

In this study, a presumptive colorimetric method was used to detect and differentiate the ova of two major soil transmitted helminths in wastewater, Ascaris and Trichuris. Gold nanoparticles were synthesised following the reduction of tetrachloroauric acid by the surface moiety of Ascaris suum, resulting in a colour change. In contrast there was no colour change with Trichuris suis indicating the absence of gold nanoparticle synthesis. Analysis of the ova using scanning electron microscopy (SEM) revealed that the synthesis of nanoparticles on the surface of ova was confirmed as gold nanoparticles (91 w/w %) by energy dispersive X-ray analysis (EDX). This study indicated that the surface moieties of helminth ova could be a potential target for ova detection and differentiation using the biosynthesis of nanoparticles by colorimetry methods. Three advantages: •Simple colorimetry based method requiring no sophisticated devices.•No trained personnel required.•Cost-effective and can be a potential candidate for biosensors.

Photoluminescence measurements of carbon quantum dots within three-dimensional hydrogel matrices using a high throughput 96 well plate method.

Solid or liquid platforms have been traditionally employed for measuring the fluorescent properties of quantum carbon dots (QCD). Hydrogels possess both liquid and solid properties which allow them to overcome several shortfalls of both solid and liquid sensing platforms. Hydrogels offer a three dimensional platform which can house nanoparticles with different attributes (i.e. fluorescent QCD's) and prevents their aggregation. Here, we incorporate QCD's (made from the hydrothermal treatment of 1-naphthylamine and citric acid) into the matrix of a zinc oxide hydrogel. This nanocomposite was shown to have hexavalent chromium (Cr6+) specific fluorescence quenching properties. Detailed fluorescence analysis of the hydrogel with Cr6+ was conducted in a high throughput manner by loading the hydrogel into wells of a black 96-well plate. Fluorescence quenching of the hydrogel-QCD-nanocomposites in the presence of dilutions of Cr6+ was measured using a fluorescence spectrophotometer and showed incremental fluorescence decreases with increasing Cr6+ concentration. Furthermore, this was quantitatively confirmed by Stern-Volmer plots showing a linear quenching trend (R2 = 0.9975) when comparing fluorescence intensities against increasing Cr6+ concentrations (0.234-1.875 µM). This technology can be applied for routine water quality testing in agricultural, natural and potable water sources for the early detection of heavy metal pollutants.

Phytofabrication of Iron Nanoparticles for Hexavalent Chromium Remediation.

Hexavalent chromium is a genotoxic and carcinogenic byproduct of a number of industrial processes, which is discharged into the environment in excessive and toxic concentrations worldwide. In this paper, the synthesis of green iron oxide nanoparticles using extracts of four novel plant species [Pittosporum undulatum, Melia azedarach, Schinus molle, and Syzygium paniculatum (var. australe)] using a "bottom-up approach" has been implemented for hexavalent chromium remediation. Nanoparticle characterizations show that different plant extracts lead to the formation of nanoparticles with different sizes, agglomeration tendencies, and shapes but similar amorphous nature and elemental makeup. Hexavalent chromium removal is linked with the particle size and monodispersity. Nanoparticles with sizes between 5 and 15 nm from M. azedarach and P. undulatum showed enhanced chromium removal capacities (84.1-96.2%, respectively) when compared to the agglomerated particles of S. molle and S. paniculatum with sizes between 30 and 100 nm (43.7-58.7%, respectively) in over 9 h. This study has shown that the reduction of iron salts with plant extracts is unlikely to generate vast quantities of stable zero valent iron nanoparticles but rather favor the formation of iron oxide nanoparticles. In addition, plant extracts with higher antioxidant concentrations may not produce nanoparticles with morphologies optimal for pollutant remediation.

Polyaromatic hydrocarbon exposure: an ecological impact ambiguity.

Polyaromatic hydrocarbons (PAHs) represent a fraction of petroleum hydrocarbons and are currently one of the foremost sources of generating energy in today's contemporary society. However, evidence highlighted in this review show that PAH pollution, as a result of oil spills, hazardous PAH-contaminated working environments and technologies which do not efficiently utilise fuels, as well as natural sources of emissions (e.g. forest fires) may have significant health implications for all taxa. The extent of damage to organisms from PAH exposure is dependent on numerous factors including degree and type of PAH exposure, nature of the environment contaminated (i.e. terrestrial or aquatic), the ability of an organism to relocate to pristine environments, type and sensitivity of organism to specific hydrocarbon fractions and ability of the organism to metabolise different PAH fractions. The review highlights the fact that studies on the potential damage of PAHs should be carried out using mixtures of hydrocarbons as opposed to individual hydrocarbon fractions due to the scarcity of individual fractions being a sole contaminant. Furthermore, potential damage of PAH-contaminated sites should be assessed using an entire ecological impact outlook of the affected area.