Tuneable redox-responsive albumin-hitchhiking drug delivery to tumours for cancer treatment.

This paper outlines a novel drug delivery system for highly cytotoxic mertansine (DM1) by conjugating to an albumin-binding Evans blue (EB) moiety through a tuneable responsive disulfide linker, providing valuable insights for the development of effective drug delivery systems toward cancer therapy.

Carbon dots as dual inhibitors of tau and amyloid-beta aggregation for the treatment of Alzheimer's disease.

Alzheimer's disease (AD) is the most common form of senile dementia, presenting a significant challenge for the development of effective treatments. AD is characterized by extracellular amyloid plaques and intraneuronal neurofibrillary tangles. Therefore, targeting both hallmarks through inhibition of amyloid beta (Aß) and tau aggregation presents a promising approach for drug development. Carbon dots (CD), with their high biocompatibility, minimal cytotoxicity, and blood-brain barrier (BBB) permeability, have emerged as promising drug nanocarriers. Congo red, an azo dye, has gathered significant attention for inhibiting amyloid-beta and tau aggregation. However, Congo red's inability to cross the BBB limits its potential to be used as a drug candidate for central nervous system (CNS) diseases. Furthermore, current studies only focus on using Congo red to target single disease hallmarks, without investigating dual inhibition capabilities. In this study, we synthesized Congo red-derived CD (CRCD) by using Congo red and citric acid as precursors, resulting in three variants, CRCD1, CRCD2 and CRCD3, based on different mass ratios of precursors. CRCD2 and CRCD3 exhibited sustained low cytotoxicity, and CRCD3 demonstrated the ability to traverse the BBB in a zebrafish model. Moreover, thioflavin T (ThT) aggregation assays and AFM imaging revealed CRCD as potent inhibitors against both tau and Aß aggregation. Notably, CRCD1 emerged as the most robust inhibitor, displaying IC50 values of 0.2 ± 0.1 and 2.1 ± 0.5 µg/mL against tau and Aß aggregation, respectively. Our findings underscore the dual inhibitory role of CRCD against tau and Aß aggregation, showcasing effective BBB penetration and positioning CRCD as potential nanodrugs and nanocarriers for the CNS. Hence, CRCD-based compounds represent a promising candidate in the realm of multi-functional AD therapeutics, offering an innovative formulation component for future developments in this area. STATEMENT OF SIGNIFICANCE: This article reports Congo red-derived carbon dots (CRCD) as dual inhibitors of tau and amyloid-beta (Aß) aggregation for the treatment of Alzheimer's disease (AD). The CRCD are biocompatible and show strong fluorescence, high stability, the ability to cross the blood-brain barrier, and the function of addressing two major pathological features of AD.

Gene Transfection Efficiency Improvement with Lipid Conjugated Cationic Carbon Dots.

An ideal vehicle with a high transfection efficiency is crucial for gene delivery. In this study, a type of cationic carbon dot (CCD) known as APCDs were first prepared with arginine (Arg) and pentaethylenehexamine (PEHA) as precursors and conjugated with oleic acid (OA) for gene delivery. By tuning the mass ratio of APCDs to OA, APCDs-OA conjugates, namely, APCDs-0.5OA, APCDs-1.0OA, and APCDs-1.5OA were synthesized. All three amphiphilic APCDs-OA conjugates show high affinity to DNA through electrostatic interactions. APCDs-0.5OA exhibit strong binding with small interfering RNA (siRNA). After being internalized by Human Embryonic Kidney (HEK 293) and osteosarcoma (U2OS) cells, they could distribute in both the cytoplasm and the nucleus. With APCDs-OA conjugates as gene delivery vehicles, plasmid DNA (pDNA) that encodes the gene for the green fluorescence protein (GFP) can be successfully delivered in both HEK 293 and U2OS cells. The GFP expression levels mediated by APCDs-0.5OA and APCDs-1.0OA are ten times greater than that of PEI in HEK 293 cells. Furthermore, APCDs-0.5OA show prominent siRNA transfection efficiency, which is proven by the significantly downregulated expression of FANCA and FANCD2 proteins upon delivery of FANCA siRNA and FANCD2 siRNA into U2OS cells. In conclusion, our work demonstrates that conjugation of CCDs with a lipid structure such as OA significantly improves the gene transfection efficiency, providing a new idea about the designation of nonviral carriers in gene delivery systems.

Low-molecular-weight aromatic acids mediated the adsorption of Cd2+ onto biochars: effects and mechanisms.

Low-molecular-weight aromatic acids (LWMAAs), a ubiquitous organic substance in natural systems, are important in controlling the environmental fate of potentially toxic metals. However, little is known about the effects of LWMAAs on the interactions between biochars and potentially toxic metals. Herein, the influences of three aromatic acids, including benzoic acid (BA), p-hydroxy benzoic acid (PHBA), and syringic acid (SA), on the adsorption of Cd2+ onto biochars generated at three different pyrolysis temperatures under acidic and neutral conditions were examined. Generally, the adsorption ability of biochars for Cd2+ improved with the increase of pyrolysis temperature, which was ascribed to the increased inorganic element contents (e.g., P, S, and Si) and aromaticity, increasing the complexation between mineral anions and metal ions, and the enhanced cation-π interaction. Interestingly, aromatic acids considerably inhibited the adsorption of Cd2+ onto biochars, which was mainly ascribed to multi-mechanisms, including competition of LWMAA molecules and metal ions for adsorption sites, the pore blocking effect, the weakened interaction between mineral anions and Cd2+ induced by the adsorbed aromatic acids, and the formation of water-soluble metal-aromatic acid complexes. Furthermore, the inhibitory effects of LWMAAs on Cd2+ adsorption intensively depended on the aromatic acid type and followed the order of SA > PHBA > BA. This trend was related to the differences in the physicochemical features (e.g., the octanol/water partition coefficient (log Kow) and molecular size) of diverse LMWAAs. The results of this study demonstrate that the effects of coexisting LMWAAs should not be ignored when biochars are applied in soil remediation and wastewater treatment.

The art of simplicity: Water-soluble porphyrin-like carbon dots self-assemble into mesmerizing red glow.

In this new study, we present an intriguing development in the field of theranostics: the simplistic self-assembly of red-emissive amphiphilic porphyrin-like carbon dots (P-CDs). By harnessing their exceptional photophysical properties, we have revealed a strong candidate as the ideal photosensitizer (PS) for applications, particularly in the realm of imaging. Spanning a remarkable size average between 1-4 nm, these particles exhibit both highly stable and unparalleled emission characteristics between 650 and 715 nm in water in comparison to current carbon dots (CDs) available. Lastly, these CDs were fairly non-toxic when tested against normal human cell lines as well as were found to have favorable imaging capabilities in zebrafish embryo.

Carbon nitride dots do not impair the growth, development, and telomere length of tadpoles.

Carbon nanoparticles, or carbon dots, can have many beneficial uses. However, we must consider whether they may have any potential negative side effects on wildlife or the ecosystem when these particles end up in wastewater. Early development stages of amphibians are particularly sensitive to contaminants, and exposure to carbon dots could disrupt their development and cause morbidity or death. Past studies have investigated short-term exposure to certain types of nanoparticles, but if these particles get into wastewater exposure may not be short term. Therefore, we tested whether chronic exposure to different concentrations of carbon dots affects the growth, metamorphosis, and telomere length of Cuban tree frog (Osteopilus septentrionalis) tadpoles. We exposed 12 groups of five tadpoles each to different concentrations of carbon dots and a control for three months and tracked survival, growth and metamorphosis. We used carbon nitride dots approximately 2 nm in size at concentrations of 0.01 mg/ml and 0.02 mg/ml, known to interrupt development in zebrafish embryos. After three months, we measured telomere length from tissue samples. We found no difference in tadpole survivorship, growth, development rate, or telomere length among any of the groups, suggesting that carbon dots at these concentrations do not disrupt tadpole development.

Mobility of antipyretic drugs with different molecular structures in saturated soil porous media.

In the post-COVID-19 era, extensive quantities of antipyretic drugs are being haphazardly released from households into the environment, which may pose potential risks to ecological systems and human health. Identification of the mobility behaviors of these compounds in the subsurface environment is crucial to understand the environmental fate of these common contaminants. The mobility properties of three broad-spectrum antipyretic drugs, including ibuprofen (IBF), indometacin (IMC), and acetaminophen (APAP), in porous soil media, were investigated in this study. The results showed that the mobility of the three drugs (the background electrolyte was Na+) through the soil column followed the order of APAP > IBF > IMC. The difference in the physicochemical characteristics of various antipyretic drugs (e.g., the molecular structure and hydrophobicity) could explain this trend. Unlike Na+, Ca2+ ions tended to serve as bridging agents by linking the soil grains and antipyretic molecules, leading to the relatively weak mobility behaviors of antipyretic drugs. Furthermore, for a given antipyretic drug, the antipyretic mobility was promoted when the background solution pH values were raised from 5.0 to 9.0. The phenomenon stemmed from the improved electrostatic repulsion between the dissociated species of antipyretic molecules and soil grains, as well as the weakened hydrophobic interactions between antipyretic drugs and soil organic matter. Furthermore, a two-site non-equilibrium transport model was used to estimate the mobility of antipyretic drugs. The results obtained from this work provide vital information illustrating the transport and retention of various antipyretic drugs in aquifers.

Biosurfactant-affected mobility of oxytetracycline and its variations with surface chemical heterogeneity in saturated porous media.

Herein, the influences of rhamnolipid (a typical biosurfactant) on oxytetracycline (OTC) transport in the porous media and their variations with the surface heterogeneities of the media (uncoated sand, goethite (Goe)-, and humic acid (HA)-coated sands) were explored. Compared to uncoated sand, goethite and HA coatings suppressed OTC mobility by increasing deposition sites. Interestingly, rhamnolipid-affected OTC transport strongly depended on the chemical heterogeneities of aquifers and biosurfactant concentrations. Concretely, adding rhamnolipid (1-3 mg/L) inhibited OTC mobility through sand columns because of the bridging effect of biosurfactant between sand and OTC. Unexpectedly, rhamnolipid of 10 mg/L did not further improve the inhibition of OTC transport owing to the fact that the deposition capacity of rhamnolipid reached its maximum. OTC mobility in Goe-coated sand columns was inhibited by 1 mg/L rhamnolipid. However, the inhibitory effect decreased with the increasing rhamnolipid concentration (3 mg/L) and exhibited a promoted effect at 10 mg/L rhamnolipid. This surprising observation was that the increased rhamnolipid molecules gradually occupied the favorable deposition sites (i.e., the positively charged sites). In comparison, rhamnolipid facilitated OTC transport in the HA-coated sand column. The promotion effects positively correlated with rhamnolipid concentrations because of the high electrostatic repulsion and deposition site competition induced by the deposited rhamnolipid. Another interesting phenomenon was that rhamnolipid's enhanced or inhibitory effects on OTC transport declined with the increasing solution pH because of the decreased rhamnolipid deposition on porous media surfaces. These findings benefit our understanding of the environmental behaviors of antibiotics in complex soil-water systems containing biosurfactants.

Advancing glioblastoma imaging: Exploring the potential of organic fluorophore-based red emissive carbon dots.

Over time, the interest in developing stable photosensitizers (PS) which both absorb and emit light in the red region (650 and 950 nm) has gained noticeable interest. Recently, carbon dots (CDs) have become the material of focus to act as a PS due to their high extinction coefficient, low cytotoxicity, and both high photo and thermal stability. In this work, a Federal and Drug Association (FDA) approved Near Infra-Red (NIR) organic fluorophore used for photo-imaging, indocyanine green (ICG), has been explored as a precursor to develop water-soluble red emissive CDs which possess red emission at 697 nm. Furthermore, our material was found to yield favorable red-imaging capabilities of glioblastoma stem-like cells (GSCs) meanwhile boasting low toxicity. Additionally with post modifications, our CDs have been found to have selectivity towards tumors over healthy tissue as well as crossing the blood-brain barrier (BBB) in zebrafish models.

Transport of dissolved organic matters derived from biomass-pyrogenic smoke (SDOMs) and their effects on mobility of heavy metal ions in saturated porous media.

Biomass-pyrogenic smoke-derived dissolved organic matter (SDOMs) percolating into the underground environment profoundly impacts the transport and fate of environmental pollutants in groundwater systems. Herein, SDOMs were produced by pyrolyzing wheat straw at 300-900 °C to explore their transport properties and effects on Cu2+ mobility in quartz sand porous media. The results indicated that SDOMs exhibited high mobility in saturated sand. Meanwhile, the mobility of SDOMs was enhanced at a higher pyrolysis temperature due to the decrease in their molecular sizes and the declined H-bonding interactions between SDOM molecules and sand grains. Furthermore, the transport of SDOMs was elevated as pH values were raised from 5.0 to 9.0, which resulted from the strengthened electrostatic repulsion between SDOMs and quartz sand particles. More importantly, SDOMs could facilitate Cu2+ transport in the quartz sand, which stemmed from forming soluble Cu-SDOM complexes. Intriguingly, the promotional function of SDOMs for the mobility of Cu2+ was strongly dependent on the pyrolysis temperature. Generally, SDOMs generated at higher temperatures exhibited superior effects. The phenomenon was mainly due to the differences in the Cu-binding capacities of various SDOMs (e.g., cation-π attractive interactions). Our findings highlight that the high-mobility SDOM can considerably affect heavy metal ions' environmental fate and transport.

Adsorption of fluoroquinolone antibiotics onto ferrihydrite under different anionic surfactants and solution pH.

To date, little information is available regarding the impacts of the widespread anionic surfactants on the adsorption behaviors of antibiotics onto typical iron oxides. Herein, we have investigated the effects of two typical surfactants (sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS)) on the adsorption of two widely used antibiotics (i.e., levofloxacin (LEV) and ciprofloxacin (CIP)) onto ferrihydrite. Results of kinetic experiments showed that the adsorption of antibiotics was well fitted by the pseudo-second-order kinetic models, indicating that the adsorption process might be controlled by chemisorption. The affinity of ferrihydrite toward CIP was greater than that toward LEV, which was ascribed to the higher hydrophobicity of CIP than LEV. Both surfactants enhanced antibiotic adsorption owing to SDS or SDBS molecules as bridge agents between ferrihydrite particles and antibiotics. Interestingly, the extent of the enhanced effects of surfactants on antibiotic adsorption declined as the background solution pH increased from 5.0 to 9.0, which was mainly due to the weaker hydrophobic interactions between antibiotics and the adsorbed surfactants on the iron oxide surfaces as well as the greater electrostatic repulsion between the anionic species of antibiotics and the negatively charged ferrihydrite particles at higher pH. Together, these findings emphasize the importance of widespread surfactants for illustrating the interactions between fluoroquinolone antibiotics and iron oxide minerals in the natural environment.

Investigation into Red Emission and Its Applications: Solvatochromic N-Doped Red Emissive Carbon Dots with Solvent Polarity Sensing and Solid-State Fluorescent Nanocomposite Thin Films.

In this work, a NIR emitting dye, p-toluenesulfonate (IR-813) was explored as a model precursor to develop red emissive carbon dots (813-CD) with solvatochromic behavior with a red-shift observed with increasing solvent polarity. The 813-CDs produced had emission peaks at 610 and 698 nm, respectively, in water with blue shifts of emission as solvent polarity decreased. Subsequently, 813-CD was synthesized with increasing nitrogen content with polyethyleneimine (PEI) to elucidate the change in band gap energy. With increased nitrogen content, the CDs produced emissions as far as 776 nm. Additionally, a CD nanocomposite polyvinylpyrrolidone (PVP) film was synthesized to assess the phenomenon of solid-state fluorescence. Furthermore, the CDs were found to have electrochemical properties to be used as an additive doping agent for PVP film coatings.

Nano-carrier for gene delivery and bioimaging based on pentaetheylenehexamine modified carbon dots.

Carbon dots (CDs) have attracted much attention due to their excellent properties and applications, especially the use for gene delivery. Considering the risks and concerns involved in the use of viral vectors for gene delivery in vivo, non-viral vectors such as CDs have gradually become an ideal alternative due to their biocompatibility and low toxicity. Therefore, in this study, the potential to apply CDs as a non-viral vector for gene delivery was investigated. The CDs were prepared using citric acid and pentaethylenehexamine (PEHA) as precursors via a one-step microwave-mediated approach. The optical, structural, and morphological properties of PEHA-derived CDs (PCDs) were characterized by ultra-violet spectroscopy (UV-vis), photoluminescence (PL), Fourier Transform Infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), zeta potential, circular dichroism spectrometry, atomic force (AFM) and transmission electron microscopies (TEM). The analysis demonstrated that the as-prepared PCDs were rich in amine groups and were positively charged. Subsequently, gel retardation assay showed that PCDs could non-covalently bind with DNA at a mass ratio of 2:1 (PCDs: DNA). Additionally, PCDs possessed a tremendously lower cytotoxicity compared with polyethylenimine (PEI), a popular precursor/dopant for many CDs preparations, and their plasmid composite showed a high transfection efficiency. Meanwhile, PCDs were also observed to cross the blood-brain barrier (BBB) by using a zebrafish model. In conclusion, these results significantly indicate that PCDs are a potential non-viral nucleic acid/gene vector to gene therapy. Also, PCDs can be utilized in drug delivery for treating brain diseases, such as Alzheimer's disease and brain tumors.

Cancer cells inhibition by cationic carbon dots targeting the cellular nucleus.

Nucleus targeting is tremendously important in cancer therapy. Cationic carbon dots (CCDs) are potential nanoparticles which might enter cells and penetrate nuclear membranes. Although some CCDs have been investigated in nucleus targeting and applied in nuclear imaging, the CCDs derived from drugs, that are able to target the nucleus, bind with DNA and inhibit the growth of cancer cells have not been reported. In this project, 1, 2, 4, 5-benzenetetramine (Y15, a focal adhesion kinase inhibitor) derived cationic carbon dots (Y15-CDs) were prepared via a hydrothermal approach utilizing Y15, folic acid and 1,2-ethylenediamine as precursors. Based on the structural, optical, and morphologic characterizations, Y15-CDs possess rich amine groups and nitrogen in structure, an excitation-dependent photoluminescence emission, and a small particle size of 2 to 4 nm. The DNA binding experiments conducted through agarose gel electrophoresis, UV-vis absorption, fluorescence emission, and circular dichroism spectroscopies, prove that Y15-CDs might bind with DNA via electrostatic interactions and partially intercalative binding modes. In addition, the cell imaging and cytotoxicity studies in human foreskin fibroblasts (HFF), prostate cancer (PC3) and osteosarcoma cells (U2OS) indicate the nucleus targeting and anticancer abilities of Y15-CDs. Most interestingly, Y15-CDs exhibit a higher cytotoxicity to cancer cells (PC3 and U2OS) than to normal cells (HFF), inferring that Y15-CDs might be potentially applied in cancer therapy.

Surfactant-mediated mobility of carbon dots in saturated soil: comparison between anionic and cationic surfactants.

Understanding the mobility, retention, and fate of carbon dots (CDs) is critical for the risk management of this emerging carbon material. However, the influences of surfactants on CDs' transport through subsurface media are still poorly understood. Herein, column experiments were conducted to explore the different influences of an anionic surfactant, sodium dodecylbenzene sulfonate (SDBS), and a cationic surfactant, cetyltrimethylammonium bromide (CTAB), on the CDs' transport in water-saturated soil. In the Na+ background electrolyte, both surfactants facilitated the transport of CDs at pH 7.0. The trend stemmed from steric hindrance, a decline in the straining effect, and competitive deposition between CDs and surfactant molecules. Additionally, SDBS increased the electrostatic repulsion of CDs and soil. Interestingly, in the divalent cation background electrolytes (i.e., Ca2+ or Cu2+), SDBS suppressed CDs' mobility, whereas CTAB had the opposite effect. The transport-inhibited effect of SDBS was mainly due to anionic surfactant ion (DBS-) precipitation with metal cations and the formation of adsorbed SDBS-Cu2+/Ca2+-CDs complexes. The enhanced effect of CTAB resulted from the CTAB coating on soil grains, which suppressed the cation bridging between CDs and soil. Furthermore, the magnitude of the SDBS promotion effect was pH-dependent. Surprisingly, CTAB could inhibit CDs' mobility at pH 9.0, owing to the binding cationic surfactant's strong hydrophobicity effect on the soil surface. Moreover, the experimental breakthrough curves of CDs were well described using a two-site transport model. Overall, the observations obtained from this study shed light on the relative mobility of CDs with different surfactants in typical groundwater conditions.

An insight into embryogenesis interruption by carbon nitride dots: can they be nucleobase analogs?

The carbon nitride dot (CND) is an emerging carbon-based nanomaterial. It possesses rich surface functional moieties and a carbon nitride core. Spectroscopic data have demonstrated the analogy between CNDs and cytosine/uracil. Recently, it was found that CNDs could interrupt the normal embryogenesis of zebrafish. Modifying CNDs with various nucleobases, especially cytosine, further decreased embryo viability and increased deformities. Physicochemical property characterization demonstrated that adenine- and cytosine-incorporated CNDs are similar but different from guanine-, thymine- and uracil-incorporated CNDs in many properties, morphology, and structure. To investigate the embryogenesis interruption at the cellular level, bare and different nucleobase-incorporated CNDs were applied to normal and cancerous cell lines. A dose-dependent decline was observed in the viability of normal and cancerous cells incubated with cytosine-incorporated CNDs, which matched results from the zebrafish embryogenesis experiment. In addition, nucleobase-incorporated CNDs were observed to enter cell nuclei, demonstrating a possibility of CND-DNA interactions. CNDs modified by complementary nucleobases could bind each other via hydrogen bonds, which suggests nucleobase-incorporated CNDs can potentially bind the complementary nucleobases in a DNA double helix. Nonetheless, neither bare nor nucleobase-incorporated CNDs were observed to intervene in the amplification of the zebrafish polymerase-alpha 1 gene in quantitative polymerase chain reactions. Thus, in conclusion, the embryogenesis interruption by bare and nucleobase-incorporated CNDs might not be a consequence of CND-DNA interactions during DNA replication. Instead, CND-Ca2+ interactions offer a plausible mechanism that hindered cell proliferation and zebrafish embryogenesis originating from disturbed Ca2+ homeostasis by CNDs. Eventually, the hypothesis that raw or nucleobase-incorporated CNDs can be nucleobase analogs proved to be invalid.

Biosurfactant-mediated mobility of graphene oxide nanoparticles in saturated porous media.

There is currently a lack of scientific understanding regarding how bio-surfactants influence the mobility of graphene oxide (GO) through saturated porous media. In this study, the transport characteristics of GO through porous media with different heterogeneities (i.e., quartz sand and goethite-coated sand) after the addition of saponin (a representative bio-surfactant) were investigated. The results demonstrated that saponin (3-10 mg L-1) promoted GO mobility in both types of porous media at pH 7.0. This trend was attributed to the competitive deposition between nanoparticles and bio-surfactant molecules for attachment sites, the enhanced electrostatic repulsion, the decreased strain, the presence of steric effects induced by the adsorbed saponin, and the increase in the hydrophilicity of nanoparticles. Intriguingly, saponin promoted GO mobility in goethite-coated sand (i.e., chemically heterogeneous porous media) to a greater extent than that in sand (i.e., relatively homogeneous porous media) when saponin concentrations increased, which stemmed from the differences in the extent of the deposition site competition for saponin on the two porous media and the electrostatic repulsion between GO and the porous media. Furthermore, a cation-bridging mechanism was also involved in the ability of saponin to increase GO mobility when the electrolyte solution was 0.1 mM Cu2+. Moreover, the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory and the colloid transport model were applicable to elucidate the mobility properties of GO with or without saponin in porous media. The findings from this work highlight the important status of bio-surfactants in the fate of colloidal carbon-based nanomaterials in subsurface systems.

Mobility of water-soluble aerosol organic matters (WSAOMs) and their effects on soil colloid-mediated transport of heavy metal ions in saturated porous media.

Water-soluble aerosol organic matters (WSAOMs) produced by biomass pyrolysis/burning can penetrate subsurface environment, and are anticipated to have a profound effect on the fate of contaminants in aquatic ecosystems. Herein, WSAOMs derived from corn straw (CS-WSAOMs) and pinewood sawdust (PW-WSAOMs) pyrolysis at 300-900 °C were utilized to investigate their mobility characteristics and impacts on the transport of heavy metal ions (i.e., Cd2+) in saturated quartz sand with or without soil colloids. This study clearly demonstrated that WSAOMs in subsurface systems exhibited high mobility, which increased as WSAOMs molecular sizes decreased and hydrogen-bond interactions between WSAOMs and sand grains declined. WSAOMs significantly improved heavy metal (i.e., Cd2+) and soil colloid-mediated Cd2+ mobility in the porous media, which stemmed from the increased binding affinities of colloids toward metal ions and the high mobility of WSAOMs. Interestingly, in terms of the mobility and colloid-facilitated transport of Cd2+, WSAOMs from higher pyrolysis temperatures exhibited enhanced effects; meanwhile, the PW-WSAOMs demonstrated stronger effects than the CS-WSAOMs. The trends were mainly attributed to the differences in the metal-binding affinities (e.g., cation-π interactions) and transport abilities of WSAOMs, as well as diverse Cd2+ adsorption capacities of colloids induced by various WSAOMs.

Insight into the effect of phosphate on ferrihydrite colloid-mediated transport of tetracycline in saturated porous media.

Colloid-mediated contaminant mobility is absolutely critical for the environmental behavior of contaminants such as antibiotics in water resources. In this study, the influences of phosphate (a commonly inorganic ligand in the environment) on the ferrihydrite colloid-mediated transport of tetracycline (TC, a typical antibiotic) in porous media were investigated. In the absence of colloids, phosphate promoted TC mobility due to the competitive deposition of phosphate and TC on the sand surface as well as the electrostatic repulsion. Interestingly, ferrihydrite colloids could inhibit TC transport; however, the inhibitory effect of the colloids was weakened by the addition of phosphate. This phenomenon stemmed from colloid-associated TC mobility, the increased electrostatic repulsion induced by adsorbed phosphate, and deposition site competition effect. Another interesting finding was that the impacts of phosphate on the colloid-mediated mobility of TC were pH-dependent. That is, phosphate exhibited a weaker effect on the inhibitory role of ferrihydrite colloids in TC mobility at pH 5.0 than that at pH 7.0; specially, ferrihydrite colloids acted as possible carriers of TC and facilitated antibiotic transport at pH 9.0. The observations were ascribed to different influences of phosphate on the binding affinity of ferrihydrite toward TC and the mobility of free TC under different pH conditions. Therefore, the findings of this study provide useful information about the fate and co-transport of antibiotics and natural mineral colloids in the presence of inorganic ligands in the aquatic environment.

Surfactants-mediated the enhanced mobility of tetracycline in saturated porous media and its variation with aqueous chemistry.

Knowledge of the mobility of tetracycline (TC) antibiotics in porous media is critical to understand their potential environmental influences. The transport characteristics of TC in sand columns with three different surfactants, including Tween 80, sodium dodecylbenzene sulfonate (SDBS), and didodecyldimethylammonium bromide (DDAB) under various conditions were investigated in this study. Results demonstrated that all surfactants enhanced TC transport under neutral conditions (10 mM NaCl at pH 7.0). The observation was attributed mostly to deposition site competition, higher electrostatic repulsion between TC molecules and sand grains, steric hindrance, and the increase of TC hydrophilicity. Furthermore, the order of the transport-enhancement effects was generally observed as follows: DDAB > SDBS > Tween 80. The trend was controlled by the variation in the physicochemical properties of surfactants. It was noticed that the presence of Cu2+ (a model divalent cation) in the background solution, the cation-bridging contributed to the promotion effects of DDAB or Tween 80 on TC mobility. Interestingly, SDBS considerably suppressed TC transport due to the precipitation of SDBS-Cu2+ complexes onto sand surfaces. Moreover, the enhancement order of surfactants at pH 5.0 was similar to that pH 7.0. However, DDAB could inhibit TC transport in sand columns at pH 9.0, which were mainly caused by the decrease of electrostatic repulsion and the hydrophobicity induced by the binding cationic surfactant. Findings from this work provide novel insight into involvement of surfactants in antibiotic transport behaviors in the subsurface environment.