Concentrations Of Target Compounds Research Articles

Sediment quality assessment combining chemical and biological (non)target analysis.

Aquatic sediments act as a storage for diverse mixtures of organic and inorganic contaminants. Nevertheless, most evaluations of contaminated sediments have been limited to the assessment of concentrations of target compounds and lethal effects on some test species. To identify the organic contaminants causing sub-lethal effects of contaminated sediment, this study combined chemical and biological (non)target analysis involving comprehensive two-dimensional gas chromatography coupled with a time-of-flight Mass Spectrometer (GCxGC/ToF-MS) analysis, embryonic malformation and high-throughput sequencing (RNA-seq) analysis on developing flounder. Polycyclic aromatic hydrocarbons were more abundant in the sediment extract of Yeongil Bay (SEY), while Jinhae Bay (SEJ) was contaminated with a large amount of unidentified chemicals. The unidentified chemicals of SEJ included branched alkanes, oxygenated cycloalkanes, heterogeneous hydrocarbons, and other unknown compounds. Percentage of pericardial edema was the highest in embryonic flounder exposed to SEY. Consistent with the morphogenesis results, the expression level of genes related to heart formation including the nkx2.5 and robo1 was greater in embryonic flounder exposed to SEY. In the analyses of differential gene expression profiles (cutoff P < 0.05), by RNA-seq, embryos exposed to SEJ showed changes related to cell differentiation, cell part morphogenesis, neurogenesis, and neuron development. Genes related to neurogenesis and positive regulation of molecular functions variated significantly in embryos exposed to SEY. These results demonstrated the advantages of combining target and non-target analysis to accurately evaluate the major chemical groups causing sediment toxicity. Therefore, this work provided a useful approach to tracking and revealing the causes of toxic effects and identifying potential toxic mechanisms.

Carboxylesterases for the hydrolysis of acetoacetate esters and their applications in terpenoid production using Escherichia coli.

Pathway engineering is a useful technology for producing desired compounds on a large scale by modifying the biosynthetic pathways of host organisms using genetic engineering. We focused on acetoacetate esters as novel low-cost substrates and established an efficient terpenoid production system using pathway-engineered recombinant Escherichia coli. Functional analysis using recombinant E. coli proteins of 18 carboxylesterases identified from the microbial esterases and lipases database showed that the p-nitrobenzyl esterase (PnbA) from Bacillus subtilis specifically hydrolyzed two acetoacetate esters: methyl acetoacetate (MAA) and ethyl acetoacetate (EAA). We generated a plasmid (pAC-Mev/Scidi/Aacl/PnbA) co-expressing PnbA and six enzymes of the mevalonate pathway gene cluster from Streptomyces, isopentenyl diphosphate isomerase type I from Saccharomyces cerevisiae, and acetoacetyl-coenzyme A ligase from Rattus norvegicus. The plasmid pAC-Mev/Scidi/Aacl/PnbA was introduced into E. coli along with plasmid expressing carotenoid (lycopene) or sesquiterpene (β-bisabolene) biosynthesis genes, and the terpenoid production was evaluated following the addition of acetoacetate esters as substrates. These recombinant E. coli strains used MAA and EAA as substrates for the biosynthesis of terpenoids and produced almost equivalent concentrations of target compounds compared with the previous production system that used mevalonolactone and lithium acetoacetate. The findings of this study will enable the production of useful terpenoids from low-cost substrates, which may facilitate their commercial production on an industrial scale in the future. KEY POINTS: • PnbA from Bacillus subtilis exhibits acetoacetate hydrolysis activity. • A plasmid enabling terpenoid synthesis from acetoacetate esters was constructed. • Acetoacetate esters as substrates enable a low-cost production of terpenoids.

Red Seaweeds as a Source of Nutrients and Bioactive Compounds: Optimization of the Extraction

The present work aimed to determine the nutritional composition (ash, protein, fat, carbohydrate content and energy value), phenolic compounds, pigments and organic acids content of three typical red algae from the Northwest of Spain: Chondrus crispus, Mastocarpus stellatus, and Gigartina pistillata; as well as their antioxidant and antimicrobial activities. Furthermore, the present work compared two extraction techniques: conventional heat assisted extraction (HAE) and high pressure assisted extraction (HPAE) to maximize the yield and the concentration of target compounds. Different independent variables were considered for the response study. Time (t) and percentage of ethanol of the solvent (S) were chosen for both techniques and temperature (T) and pressure (P) were used for HAE and HPAE, respectively. The experiments were designed following a response surface methodology (RSM) approach. The obtained results showed a similar nutritional composition between algae samples: low-fat content and high content of proteins, carbohydrates and energy. All tested algae showed good antioxidant and antimicrobial properties. Finally, HEA demonstrated to be the most efficient extraction technique. This study confirms the potential of red algae to be part of the human diet as a source of non-animal protein, due to its nutritional content, phenolic profile, pigments concentration and bioactive properties, which proves that HAE is the optimum technique for the extraction maximization.

Calibration-Curve-Locking Database for Semi-Quantitative Metabolomics by Gas Chromatography/Mass Spectrometry.

Calibration-Curve-Locking Databases (CCLDs) have been constructed for automatic compound search and semi-quantitative screening by gas chromatography/mass spectrometry (GC/MS) in several fields. CCLD felicitates the semi-quantification of target compounds without calibration curve preparation because it contains the retention time (RT), calibration curves, and electron ionization (EI) mass spectra, which are obtained under stable apparatus conditions. Despite its usefulness, there is no CCLD for metabolomics. Herein, we developed a novel CCLD and semi-quantification framework for GC/MS-based metabolomics. All analytes were subjected to GC/MS after derivatization under stable apparatus conditions using (1) target tuning, (2) RT locking technique, and (3) automatic derivatization and injection by a robotic platform. The RTs and EI mass spectra were obtained from an existing authorized database. A quantifier ion and one or two qualifier ions were selected for each target metabolite. The calibration curves were obtained as plots of the peak area ratio of the target compounds to an internal standard versus the target compound concentration. These data were registered in a database as a novel CCLD. We examined the applicability of CCLD for analyzing human plasma, resulting in time-saving and labor-saving semi-qualitative screening without the need for standard substances.

Occurrence of plant secondary metabolite fingerprints in river waters from Eastern Jutland, Denmark

BackgroundA large number of chemicals are constantly introduced to surface water from anthropogenic and natural sources. So far, unlike anthropogenic pollutants, naturally occurring compounds are not included in environmental monitoring programs due to limited knowledge on their occurrence and effects in the environment. Since previous studies suggest that natural compounds might contribute to mixture risks in aquatic ecosystems and for drinking water production, there is a need to increase empirical evidence on the occurrence of these compounds in aquatic systems. To this end, we performed target screening on 160 toxic secondary plant metabolites (PSMs), prioritized in silico for their likelihood of occurrence, persistence, toxicity and mobility in river waters, using liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). The samples were collected during rain events from three Danish rivers from an area covered by grassland, forest and agricultural crops.ResultsIn total, 27 targets belonging to different compound classes such as alkaloids, coumarins and flavonoids were detected, among them 12 compounds, which have not been reported in surface waters before. The most prominent compound class was the group of alkaloids with 41% of the detected targets, many of them detected in more than 80% of the samples. Individual compound concentrations were up to several hundred ng/L with the neurotoxic alkaloid coniine from poison hemlock and the flavonoid daidzein reaching maximum concentrations of about 400 and 282 ng/L, respectively. In some samples, especially from Vejle river, the rise in concentration of target compounds were associated with increase in the rain intensity and elevated water table in the river.ConclusionsThe measured natural toxin concentrations are well within the range of those of synthetic environmental contaminants and need to be considered for the assessment of potential risks on aquatic organisms and drinking water production.

Monitoring E. coli Cell Integrity by ATR-FTIR Spectroscopy and Chemometrics: Opportunities and Caveats

During recombinant protein production with E. coli, the integrity of the inner and outer membrane changes, which leads to product leakage (loss of outer membrane integrity) or lysis (loss of inner membrane integrity). Motivated by current Quality by Design guidelines, there is a need for monitoring tools to determine leakiness and lysis in real-time. In this work, we assessed a novel approach to monitoring E. coli cell integrity by attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. Various preprocessing strategies were tested in combination with regression (partial least squares, random forest) or classification models (partial least squares discriminant analysis, linear discriminant analysis, random forest, artificial neural network). Models were validated using standard procedures, and well-performing methods were additionally scrutinized by removing putatively important features and assessing the decrease in performance. Whereas the prediction of target compound concentration via regression was unsuccessful, possibly due to a lack of samples and low sensitivity, random forest classifiers achieved prediction accuracies of over 90% within the datasets tested in this study. However, strong correlations with untargeted spectral regions were revealed by feature selection, thereby demonstrating the need to rigorously validate chemometric models for bioprocesses, including the evaluation of feature importance.

Effects of persulfate and hydrogen peroxide on oxidation of oxalate by pulsed corona discharge

Application of gas-phase pulsed corona discharge (PCD) to oxidation of aqueous pollutants shows unequalled energy efficiency among advanced oxidation processes (AOPs). Improved AOPs often activate extrinsic oxidants. Experimental research was undertaken into sodium persulfate and hydrogen peroxide activation by PCD in oxidation of 1.11 mM oxalate. Oxidant and target compound concentration ratios, pH, gas-liquid contact surface and pulse repetition frequency were studied as control parameters. Results implicated a beneficial effect at oxalate/persulfate molar ratios from 1:0.1 to 1:1 in acidic medium with the optimum at 1:0.5, moderate contact surface and lower frequency. However, the observed synergism of PCD/PS combination decreased with increasing the initial pH of the treated solution. Hydrogen peroxide exhibited negative or neutral impact in all media. Non-assisted PCD proved the most energy efficient approach towards water treatment at neutral and alkaline conditions.

Multilabel Per-Pixel Quantitation in Mass Spectrometry Imaging.

In quantitative mass spectrometry imaging (MSI), the gold standard adds a single structural homologue of the target compound at a known concentration to the sample. This internal standard enables to map the detected intensity of the target molecule against an external calibration curve. This approach, however, ignores local noise levels and disproportional ion suppression effects, which might depend on the concentration of the target compound. To overcome these issues, we propose a novel approach that applies several isotopically labeled versions, each at a different concentration, to the sample. This allows creating individual internal calibration curves for every MSI pixel. As proof of principle, we have quantified an endogenous peptide of histone H4 by matrix-assisted laser desorption/ionization-Q-MSI (MALDI-Q-MSI), using a mixture of three isotopically labeled versions. The usage of a fourth label allowed us to compare the gold standard to our multilabel approach. We observed substantial heterogeneity in ion suppression across the tissue, which disclosed itself as varying slopes in the per-pixel regression analyses. These slopes were histology-dependent and differed from each other by up to a factor of 4. The results were validated by liquid chromatography–mass spectrometry (LC-MS), exhibiting a high agreement between LC-MS and MALDI-Q-MSI (Pearson correlation r = 0.87). A comparison between the multilabel and single-label approaches revealed a higher accuracy for the multilabel method when the local target compound concentration differed too much from the concentration of the single label. In conclusion, we show that the multilabel approach provides superior quantitation compared to a single-label approach, in case the target compound is inhomogeneously distributed at a wide concentration range in the tissue.

Simultaneous determination of methanol, ethanol and isopropanol in human blood and white spirit samples

A simple and cost-effective method for simultaneous determination of methanol, ethanol, and isopropanol in human blood and white spirit samples using headspace gas chromatography coupled with flame ionization detection (HS-GC-FID) was developed and validated for clinical and toxicological purposes. In this study, the headspace sampling procedure was investigated, indicating optimized temperature of 70 &amp;deg;C in 20 min. Concentrations of target compounds were determined by internal standard (IS) method with acetonitrile as IS compound. A good resolution of chromatographic peaks was achieved. The linear ranges for all the compounds were from 1 to 500 mg/dL. Our method was validated with adequate accuracy (recovery &amp;gt; 98%) and precision (RSD &amp;lt; 0.1%) in whole human blood and white spirit samples. The limits of detection were below 0.5 mg/L for the three compounds. This method is easy to perform, making it suitable for routine analysis in clinical biochemistry and forensic laboratories.

Occurrence, spatiotemporal distribution and potential ecological risks of antibiotics in Dongting Lake, China

We investigated the occurrence and distribution of 18 antibiotics in surface water from Dongting Lake, as well as in influents and effluents from a municipal wastewater treatment plant (WWTP) and a swine farm. The total concentrations of target antibiotics in surface water ranged from limit of quantification to 3107 and 5.32-107ngL-1 in the dry season and wet season, respectively. Among these studied antibiotics, ciprofloxacin (CIP) and lomefloxacin were as the main components in the dry season, while CIP, oxytetracycline, and chlortetracycline were the main components in the wet season. The concentrations of target compounds exhibited obvious temporal-spatial variation characteristic in the studied region, suggesting their different emission sources related to pig breeding, aquaculture, and humanactivities, as well as possible degradation in the aquatic system. We estimated that the daily total input and output masses of antibiotics in the influent and effluent from the swine farm were 12.1mg d-1 pig-1 and 7.49μg d-1 pig-1, while they were 103μg d-1 inhabitant-1 and 22.9μg d-1 inhabitant-1 in the WWTP. The risk assessment results indicated that CIP posed a moderate or high risk to algae in most locations in Dongting Lake.

Rapid and practical qualitative and quantitative evaluation of non-fumigated ginger and sulfur-fumigated ginger via Fourier-transform infrared spectroscopy and chemometric methods

A strategy was developed to distinguish and quantitate nonfumigated ginger (NS-ginger) and sulfur-fumigated ginger (S-ginger), based on Fourier transform near infrared spectroscopy (FT-NIR) and chemometrics. FT-NIR provided a reliable method to qualitatively assess ginger samples and batches of S-ginger (41) and NS-ginger (39) were discriminated using principal component analysis and orthogonal partial least squares discriminant analysis of FT-NIR data. To generate quantitative methods based on partial least squares (PLS) and counter propagation artificial neural network (CP-ANN) from the FT-NIR, major gingerols were quantified using high performance liquid chromatography (HPLC) and the data used as a reference. Finally, PLS and CP-ANN were deployed to predict concentrations of target compounds in S- and NS-ginger. The results indicated that FT-NIR can provide an alternative to HPLC for prediction of active components in ginger samples and was able to work directly on solid samples.

Effects of recycling on the aqueous two-phase extraction of bioactives from haskap leaves

Aqueous two-phase extraction (ATPE) is an emerging technique that integrates separation, concentration, and partial purification of target compounds from natural resources. One potential issue which may prevent industrial application of ATPE, is the large consumption of phase-forming components such as alcohol, polymers, salt, and sugar. On top of that, post-handling and disposal of these components will increase associated costs. This research evaluated the effects of recycling ATPE components on the extraction of bioactive compounds from haskap (Lonicera caerulea) leaves. In this work, the ATPE systems were combinations of ammonium sulphate/ethanol, sodium dihydrogen phosphate/ethanol, glucose/1-propanol, and maltose/1-propanol. Total phenolic content (TPC), flavonoids, and chlorogenic acid were assessed in terms of their partitioning behavior, extraction efficiencies, and yields. The results showed that with two recycling stages, the extraction performance for all four ATPE systems was maintained. The average TPC extraction efficiencies across the first extraction stage and two recycling stages were 91.4% for ammonium sulphate/ethanol, 99.6% for sodium dihydrogen phosphate/ethanol, 85.1% for glucose/1-propanol, and 85.0% for maltose/1-propanol systems. This suggests that recycling could make ATPE a more sustainable technique in recovering high-value compounds from natural resources.

Comparative study of degradation of toluene and methyl isobutyl ketone (MIBK) in aqueous solution by pulsed corona discharge plasma

Effectiveness of pulsed power plasma for the degradation of two toxic volatile organic compounds (VOCs), toluene and methyl isobutyl ketone (MIBK), in aqueous solution was evaluated. The plasma degradation of MIBK has been studied for the first time. The influence of initial concentration of target compound, solution pH and scavengers on percentage degradation was evaluated. 100% removal of 200 mg/L of toluene and MIBK was achieved both in liquid and gaseous phases after 12 and 16 min of plasma treatment, respectively. The first order rate constant of toluene and MIBK degradation (for 200 mg/L each) was 0.421 and 0.319 min−1 respectively when they were treated individually, and these values decreased slightly during degradation of their mixture. MIBK degradation was slower than toluene and it might be due to semi volatile and hydrophilic nature of MIBK. The effect of initial concentration of toluene and MIBK showed different degradation patterns. Highest degradation of both the compounds was obtained in neutral pH and in absence of scavengers. •OH radical was the major reactive species involved in their degradation. Their degradation in real environmental matrices showed that removal reduced significantly in secondary effluent due to scavenging of reactive species by various ions and organic matter. The total number of degradation intermediates identified in case of toluene and MIBK was 11 and 14 respectively and formate was the one recalcitrant byproduct generated. The degradation pathway of toluene and MIBK involving reactions of reactive oxygen and nitrogen species and reductive species is proposed.

Sex-related differences in disposition of sulfamethoxazole, N-acetyl-sulfamethoxazole and trimethoprim in yellow catfish (Pelteobagrus fulvidraco) following a single oral administration

The aim of this present study was to explore the sex-related differences in disposition regularities of sulfamethoxazole (SMZ), N-acetyl-sulfamethoxazole (N-ac-SMZ) and trimethoprim (TMP) in male and female yellow catfish. Concentrations of target compounds were determined using a reliable HPLC-MS/MS approach, which was validated according to the guidelines defined by FDA. The results showed that there are significant sex-associated differences in SMZ concentrations of muscle with skin and liver, in N-ac-SMZ levels of muscle with skin and kidney, and in TMP concentrations of muscle with skin, liver and kidney. Whereas, no significant sex differences were also observed in SMZ, N-ac-SMZ and TMP levels of plasma, in SMZ concentrations of kidney and in N-ac-SMZ concentrations of liver. Longer residue time of N-ac-SMZ than SMZ was observed in male and female yellow catfish. Withdrawal time (WT) of SMZ (N-ac-SMZ as the marker residue) calculated by the WT 1.4 software, was 11 days (male) and 9 days (female), respectively. By contrast, WT of SMZ (SMZ as the marker residue) was 9 days (male) and 7 days (female), respectively. These results could serve as reference data for establishing disparate use regimen and drug withdrawal time of SMZ and TMP in male and female yellow catfish.

Multiple classes of chemical contaminants in soil from an e-waste disposal site in China: Occurrence and spatial distribution

E-waste recycling is well known for releasing halogenated organic compounds (HOCs) and heavy metals. This study investigated the occurrence and distribution of traditional and novel classes of contaminants, including chlorinated, brominated, and mixed halogenated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs, PBDD/Fs, PXDD/Fs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and polyhalogenated carbazoles (PHCZs), in soil from an e-waste disposal site in Hangzhou. PBDEs were the most abundant, at 343–69306 ng kg−1, followed by PHCZs (896–41,362 ng kg−1), PCDD/Fs (349–19,396 ng kg−1), PCBs (51.3–1834 ng kg−1), PBDD/Fs (2.99–524 ng kg−1) and PXDD/Fs (0.104–21.2 ng kg−1). The detected target compound concentrations were generally lower than those reported in the literature for informal e-waste sites. Nevertheless, they can serve as a basis of information for evaluation and subsequent control. The toxic equivalent (TEQ) contributions from these contaminants (except PBDEs) decreased as follows: PCDD/Fs > PXDD/Fs > PHCZs > PCBs > PBDD/Fs. ΣDioxins (PCDD/Fs + PBDD/Fs + PXDD/Fs) accounted for 47.7%–97.2% of the total TEQs in the soil. OCDD, 1,2,3,4,6,7,8-HpBDF and OBDF were the dominant congeners, mainly derived from combustion and transport because of their low saturated vapor pressure. PXDFs were more abundant than PXDDs, and homologue profiles suggested a similar formation mechanism for PXDFs and PBDFs involving successive Br-to-Cl exchange. PHCZs were reported in soil from an e-waste disposal area for the first time, and their concentrations were several orders of magnitude higher than those of the other contaminants. Although the risk of human exposure in this study was estimated to be lower than the values recommended by the WHO (1–4 pg TEQ/kg bw/day), health implications still exist, and further investigations are necessary.

A novel in-situ passive sampling technique in the application of monitoring diuron in the aquatic environment

Abstract Diuron is one of the most common herbicides used in agriculture with long persistence and high toxicity causing a certain hazard to the environment. Thus, this is necessary to control the residue levels of diuron in a natural environment. To achieve this goal, a diffusive gradient in thin-films technique (DGT), as a new method for in-situ sampling, is described in this paper, which can provide the time-weighted average concentration of target compounds in the sampling period. DGT consists of XAD18 resin gel can accumulate up to 73.58 ug diuron in lab conditions and without significant negative performance under varies range of pH (4 to 9), ionic strength (0.001 to 0.5 mmol L−1) and dissolved organic matter(0–20 mg L−1). The string rate of more than 100 rpm indicated the DGT will not likely be affected by flow rate in the aquatic environment. The study successfully indicates the DGT’s performance on diuron, providing a promising technique for future investigation of distribution and occurrence in the natural environment.

Polycyclic aromatic hydrocarbons and their nitro-derivatives in urban road dust across China: Spatial variation, source apportionment, and health risk

As an essential carrier of hazardous substances, fugitive road dust has become a severe issue in China. In this study, 212 road dust samples from 53 cities in China were collected to comprehensively investigate the spatial variations, potential sources, and cancer risk of 16 polycyclic aromatic hydrocarbons (PAHs) and 16 nitro-PAHs. The total PAHs concentrations ranged from 0.07 to 345 μg/g dry weight, which is at a moderate level compared to other regions in the world. The mean concentration of Σ16nitro-PAHs was 111 ± 115 ng/g, which is 2–3 orders of magnitude lower than that of Σ16PAHs. A clear geographical trend of dust PAHs and nitro-PAHs was observed in the northeast, north, and east coastal regions of China at a higher level. Moreover, a significant correlation between latitude and PAHs/nitro-PAHs revealed the influences of outdoor temperature and coal combustion for heating in the different regions on the emission and reaction of PAHs and nitro-PAHs. The secondary formation of most nitro-PAHs increases with a decrease in latitude indicated that solar radiation and temperature are important factors on secondary formation of nitro-PAHs. The average concentration of total PAHs and their derivatives in trunk road samples were statistically higher than those in other road samples (p < 0.05), indicating the influence of traffic load on target compound concentration. Generally, the primary sources of PAHs in the road dust samples were coal combustion (23.9%), vehicles (57.1%), and wood/biomass combustion (19.0%). For nitro-PAHs, the main sources were secondary formation (30.9%), biomass/coal combustion (28.4%), and vehicles (44.9%). Furthermore, a moderate potential carcinogenic risk due to PAHs and nitro-PAHs in the dust samples was found in China.

Extraction of phytosterols and tocopherols from rapeseed oil waste by supercritical CO2 plus co-solvent: A comparison with conventional solvent extraction

In the present study, modified extraction methods using supercritical CO2 were investigated in order to obtain high-added value compounds from rapeseed oil deodorizer distillate and comparisons were done with modified Soxhlet extraction (solvent extraction + silica). For supercritical fluid extraction (SFE), the optimal extraction parameters were temperature of 40 °C, pressure of 350 bar (for phytosterols), 400 bar (for tocopherol), 5 wt% ethanol as co-solvent, and saponification pretreatment. The optimized SFE procedure led to the recovery of three main phytosterols (50 wt % β-sitosterol, 23.91 wt % Brassicasterol, and 36.25 wt % Campesterol) and only α-tocopherol. Moreover, there was no synergistic effect with saponification pretreatment + co-solvent and the efficiency and concentration of target compounds were less than supercritical CO2 + co-solvent. Also, comparative Data showed that the efficiency of phytosterols and tocopherols was approximately three times higher (p < 0.05) in SFE relative to modified Soxhlet extraction. Furthermore, the use of ethanol (5 wt %) as co-solvent, improved phytosterols and tocopherol efficiency and purity. The SFE technique offers various advantages over the modified Soxhlet extraction technique, including increasing the solubility of tocopherols and sterols by using CO2+ co-solvent, minimized usage of toxic organic solvents and increased purity of extracted products.

Coexposure Degradation of Purine Derivatives in the Sulfate Radical-Mediated Oxidation Process

Purines are the most widely occurring heterocyclic-N compounds. The degradation behaviors of purine derivatives, theophylline (TPL) and adenine (ADN) as representatives, in both single-component and mixture systems during UV/peroxydisulfate (PDS) treatment were explored. In the mixture system when the concentrations of SO4•- and HO• were reduced by more than half in comparison to a single-component system, the observed first-order rate constant of TPL was reduced by 11%, whereas ADN degradation was almost completely inhibited. An ADN "revert" pathway, that is, back transformation of ADN(-H)• to ADN by TPL via single electron-transfer reactions, was found. The second-order rate constant of ADN(-H)• with TPL was determined to be (1.94 ± 0.21) × 108 M-1 s-1. A kinetic model was developed, which successfully quantifies the contribution of each reaction pathway at various target compound concentrations. In the copresence of 0.1 μM TPL, 58% ADN (3.0 μM) was reduced back to ADN at the PDS dose of 290 μM. The ADN revert pathway's effectiveness is governed by the relative reduction potentials of the reactants. Purines and phenols with lower reduction potentials are able to react via the ADN revert pathway. These findings improve the understanding of the removal of mixture pollutants from real water media in advanced oxidation processes.

Core-Shell-Heterostructured Magnetic-Plasmonic Nanoassemblies with Highly Retained Magnetic-Plasmonic Activities for Ultrasensitive Bioanalysis in Complex Matrix.

Herein, a facile self‐assembly strategy for coassembling oleic acid‐coated iron oxide nanoparticles (OC‐IONPs) with oleylamine‐coated gold nanoparticles (OA‐AuNPs) to form colloidal magnetic–plasmonic nanoassemblies (MPNAs) is reported. The resultant MPNAs exhibit a typical core–shell heterostructure comprising aggregated OA‐AuNPs as a plasmonic core surrounded by an assembled magnetic shell of OC‐IONPs. Owing to the high loading of OA‐AuNPs and reasonable spatial distribution of OC‐IONPs, the resultant MPNAs exhibit highly retained magnetic–plasmonic activities simultaneously. Using the intrinsic dual functionality of MPNAs as a magnetic separator and a plasmonic signal transducer, it is demonstrated that the assembled MPNAs can achieve the simultaneous magnetic manipulation and optical detection on the lateral flow immunoassay platform after surface functionalization with recognition molecules. In conclusion, the core–shell‐heterostructured MPNAs can serve as a nanoanalytical platform for the separation and concentration of target compounds from complex biological samples using magnetic properties and simultaneous optical sensing using plasmonic properties.